Environmentally-neutral processing with condensed phase cryogenic fluids

ABSTRACT

Systems, methods and apparatus are provided for utilizing a substantially condensed phase cryogenic fluid for the purpose of remediation and retrieval of, e.g., spilled crude oil and other “oil spill”-related products from marine/aquatic and terrestrial environments. In some implementations, systems and apparatus are provided for applying a substantially condensed phase cryogenic fluid to a volume of spilled oil, and further having structure for collecting the spilled oil. Some implementations are environmentally-neutral. Substances other than oil may be remediated as well.

TECHNICAL FIELD

This disclosure relates to environmentally-neutral processing withcondensed phase cryogenic fluids (CPCF).

BACKGROUND

In the wake of the 1989 Exxon Valdez oil spill, numerous measures weretaken in attempt to cleanup the spill. A trial burn was conducted duringthe early stages of the spill, in a small region of the spill isolatedfrom the rest by a fire-resistant boom. The test was of questionablesuccess, and because of unfavorable winds and weather (e.g., regionalmeteorological dynamics), and the negative potential impact on airquality and the general environment (e.g., as effects to Nature) noadditional burning was attempted during the next 16 years of this(ongoing) cleanup effort. Mechanical cleanup was started shortlyafterwards using booms and skimmers, but technical problems due to thethickness of the oil layer and kelp that tended to clog the equipment,became a serious issue. On Mar. 24, 1989, a private company was retainedto apply a dispersant, using a helicopter and dispersant buckets. Theresults and/or findings showed, however, that there was insufficientwave action to mix the oil and the dispersant, and use of this methodwas also discontinued. Degradation and byproducts from additivedispersants and/or reactions with oil constituents and petroleumderivatives, became a concern to many. Another concern arose from thefact that the skimmers could not be made readily available during thecritical first 24 hours after the spill, i.e., a crucial period forresponse time, in dealing with wildlife and fragile ecosystems.

Working with the U.S. Coast Guard, who officially led the response,Exxon mounted a cleanup effort that is said to have exceeded in cost,scope, and thoroughness, any previous oil spill cleanup operation. Inaddition to the Exxon employees, more than 11,000 Alaska residentsworked throughout the region, helping to restore the environment. Threeyears after the event of the spill, in 1992, the Coast Guard declaredthe cleanup complete. However, to this day, many environmental problemsremain, and wildlife are still recovering from this disaster.

The Exxon-Valdez case, along with the standard practices for dealingwith oil-spills, and the results of clean-up operations and remediationefforts in subsequent spills, indicate that the current methodologiesand technologies used in dealing with spills of crude oil and itsderivatives are far from ideal. The impacts to our environment and localecology, resulting from oil-spills, are significant, and remain aserious problem.

The problem, to a large degree, is due to the natural properties of theoil or pollutant substrate itself: its immiscibility, its tendency todisperse over aqueous surfaces (or to form thin films), its viscosity(e.g., that results in the smothering of aquatic birds and mammals, orclinging to coastal rocks), its potential toxicity, and the natureand/or longevity of these pollutant effects. Additionally, spilled oilscan vary from low viscosity fluids containing (in various parts)volatile and/or combustible moieties, to highly-viscous and very gummyor tar-like products. Thus, oil and other immiscible pollutantsubstances are difficult to handle and effectively remove, both from thebody of water where the spill occurs, and from surrounding environmentalareas, e.g., beaches, rocks, and other natural habitats.

SUMMARY

In an aspect of the invention, system, method and/or apparatus areprovided for utilizing a substantially condensed phase cryogenic fluidfor the purpose(s) of clean-up, retrieval, and/or removal of, e.g.,spilled crude oil, processed oils, petroleum byproducts and derivatives,lipid-based pharmaceuticals, reactive chemicals, toxic or noxious waste,and/or spills of other hydrophobic or immiscible products frommarine/aquatic and terrestrial environments, and the remediation ofthose environments. Substances other than oil may be remediated as well.In some implementations, designs for vessels, remediation systems,sparging units and other apparatus are provided for use in the delivery,distribution, and/or application of the substantially condensed phasecryogenic fluid to a volume of spilled oil or other immisciblesubstance, along with structures for collecting, storing, and removingthe sequestered oil or other materials spilled, and instruments for“real-time” testing/monitoring of spill conditions, pollutant wastes,and/or efficiency of the remediation operation. Some implementations areenvironmentally-neutral.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 illustrates an example of a remediation system.

FIG. 2 illustrates certain characteristics of liquid nitrogen.

FIG. 3 illustrates an example of a method for remediation.

FIG. 4 illustrates an example of a hub.

FIG. 5 illustrates an example of an apparatus for dispensingcondensed-phase cryogenic fluid (“CPCF”).

FIG. 6 illustrates an example of an apparatus for dispensing CPCF.

FIG. 7 illustrates an example of an apparatus for dispensing CPCF.

FIG. 8 illustrates an example of an apparatus for dispensing CPCF.

FIG. 9 illustrates an example of an apparatus for dispensing CPCF.

FIG. 10 illustrates an example of an apparatus for dispensing CPCF.

FIG. 11 illustrates an example of an apparatus for dispensing CPCF.

FIG. 12 illustrates an example of an apparatus for dispensing CPCF.

FIG. 13 illustrates an example of a remediation apparatus.

FIGS. 14A and 14B illustrate an example of a remediation apparatus.

FIG. 15 illustrates an example of a remediation apparatus.

FIG. 16A illustrates an example of a remediation apparatus.

FIG. 16B illustrates an example of a remediation apparatus.

FIG. 17 illustrates an example of a remediation apparatus.

FIG. 18A illustrates an example of a remediation apparatus.

FIG. 18B illustrates an example of a remediation apparatus.

FIG. 18C illustrates an example of an apparatus for dispensing CPCF.

FIGS. 19A-19D illustrate an example of a waste tank.

FIG. 20 illustrates an example of a remediation apparatus.

FIGS. 21 and 22 illustrate viscous agglomeration, accretion andencapsulation, and sequestration by lattice uptake.

DETAILED DESCRIPTION

The following is a description of preferred implementations, as well assome alternative implementations, of systems, methods and apparatus forenvironmentally-neutral processing using substantially condensed phasecryogenic fluids (CPCF). An environmentally-neutral technology orremediation operation may be considered one that neither employs as anactive agent in any clean-up process or remediation operation, nortransports to the spill site or remediation environment for use as suchan active agent, any material that is not natural or “normal to” (i.e.,normally found in), and/or already present in that environment orecosystem.

Moreover, this disclosure relates to, e.g., the clean-up of crude oil,processed oils, and other forms of spilled oils, lipid-basedpharmaceuticals, and/or other hydrophobic or immiscible substances; itfurther relates to such corollary areas as containment, confinement, andremoval of such hazardous pollutant and/or spilled substrates; as wellas certain methodologies for critical response in cases of terroristthreats, and/or events involving deployment of harmful reactivechemicals, radiological, and/or biological agents.

CPCF such as the saturated liquid states or condensed phases ofliquefied air, liquefied nitrogen, liquefied helium, argon, etc. canprovide viable methods for use in oil-spill clean-up and retrievaloperations, environmental remediation, and other applications.

Processes using CPCF have multiple applications in the remediation ofsmall-to-large scale spills of crude oil, hydrocarbons and petroleumbyproducts, and/or other immiscible substrates (as noted above, anddiscussed further below) from the open oceans, coastal waters, inlandwaterways, and other marine or aquatic bodies. CPCF processes are alsowell-suited for use in fragile ecosystems and boundary areas, e.g.,ranging from estuaries, wetlands, and wildlife preserves, to beaches,parks, and rocky shoreline areas, as well as for terrestrial areas(where they are applicable for both miscible and immiscible substances),e.g. refineries, power plants, pipelines, airports. Other independentapplications are for extinguishing oil-well and oil-field fires,incendiaries, and extreme (high intensity or high velocity fires); indealing with hazardous corrosive and/or reactive chemicals, noxious andtoxic waste, as well as harmful biological, chemical, and radiologicalagents, e.g., caused by willful deployments and/or terrorist threats.

A feature common to CPCF techniques, in some implementations, is thatthe methods, systems and apparatus are environmentally-neutral.Environmental neutrality, or environmentally-neutral remediation isconsistent with sustainability. Put another way, anenvironmentally-neutral process or remediation operation neither employsas an active agent in any clean-up process or environmental remediationoperation, nor transports to spill site for use as an active remediant,any material that is not natural or “normal” to (i.e., normally found tobe present) and/or already present in that environment or ecosystem.

For example, some techniques utilize liquefied nitrogen and/or liquefiedair. Only the phase, or state, from a gas to a condensed liquid, ischanged. The mere introduction of air (or re-introduction of the airthat has been liquefied) leaves behind nothing that is not “normal” tothat environment, and/or that was not already in the ecosystem.Likewise, nitrogen is the predominant component of air, and therefore,its presence also is environmentally-neutral. In some implementations,the liquefied nitrogen or liquefied air is made on-site.

Overview and Fundamentals

The following includes a description of some general principles relevantto some implementations, and some potentially relevant scientific basesfor those general principles.

Generally speaking, low temperature liquefied gases (e.g., liquid air,nitrogen, carbon dioxide, neon, argon, helium) can be used to freeze oiland other immiscible substances which have been spilled into a saltwater (e.g., oceanic) or fresh water (e.g., aquatic) environment. Animportant issue, however, is whether or not oil or immiscibles frozen bysuch a method will remain in a solid form long enough for it to beeffectively handled and removed from the spill area in an economical andtechnologically viable manner. Given the thermodynamic, fluidmechanical, chemical, and physical properties of the substances involved(e.g., the spilled oil or immiscible substrate, the resultant viscous orsolid product, the fluid and thermodynamic properties of the waterenvironment, and effects of the addition of cryogenic fluids upon it,the qualitative physical properties of the various cryogenic gases,etc.), particular methods, systems and apparatus are disclosed for usingand applying condensed phase cryogenic fluid (“CPCF”) to the spill areaand retrieving the solid mixed phase (frozen ice-oil) or solid compositeof water-ice and an immiscible pollutant.

Given the relevant chemical and thermodynamic properties, mostimplementations, facilitate the delivery and distribution of a saturatedliquid or condensed phase cryogenic fluid (e.g., liquefied nitrogen in asaturated-liquid state). It is desirable, in most implementations, tomaximize the percentage of condensed phase cryogenic fluid distributedto the spilled oil. One manner of achieving this is delivering the CPCFto the substrate at atmospheric pressure. Based upon these chemical andthermodynamic properties, the availability, ease/difficulty ofproduction and transportation, and the relative costs of applicablecryogenic fluids, most implementations utilize the saturated liquid orcondensed phase of liquefied nitrogen and/or liquefied air. Both ofthese can be either produced directly at the spill site (e.g., on boarda suitable vessel or barge) or transported to the spill site (e.g., intankers, via helicopters and aircraft, by trucks, or otherwise).

Delivering a saturated liquid or condensed phase cryogenic fluid causessignificant chemical and physical changes in the hydrophobic substrates(e.g., crude oils, crude or processed oil byproducts, hydrocarbons andpetroleum derivatives, lipids or other immiscible substrates), in thelattice structure of the water ice, and/or the solid phase dynamics ofthe frozen ice-oil composite. These changes may suggest the role ofhydrophobicity in the viscous agglomeration, accretion andencapsulation, and/or sequestration by lattice uptake, of suchhydrocarbons, lipids and/or immiscibles, as well as in the maximizationof the ‘oil’-to-water ratio in the cleanup and remediation of thesespilled oils and immiscible substrates from marine/aquatic bodies,terrestrial systems, beaches and rocky shorelines, and estuarine andother fragile ecosystems (e.g., wetlands and migratory wildliferefuges). Such processing via use of CPCF in land-based or terrestrialsystems, however, is not in any way limited or constrained tohydrophobic or immiscible substances, and is applicable generally.

The chemical and/or physical changes are cryogenically induced in theenvironment to affect: a) the hydrophobic substrates (e.g. crude oils)or immiscibles being remediated, in terms of substantial increases inthe viscosity and mean density (thus resulting in the observed increasesin manageability) of these substrates via hydrophobic effects; b) thestructure of the bulk ‘water’ ice, as it undergoes lattice changes;and/or c) the solid phase dynamics of the mixed-state (frozen) oil-icecomposite. The nature of the frozen oil-ice composite is affected by thestructure of the bulk water ice as it goes through several latticechanges. At least two of these lattice changes relate to changes in thecrystalline form (geometry) of the ice, whereas two are transitions toamorphous solid states. Such changes are a function of the rapiddecrease in temperature produced via the application of the saturatedliquid phase of a cryogenic fluid (e.g., liquefied nitrogen or air thatis in a liquid state rather than a vapor or mixed-state). These changesmay be induced to facilitate clean-up of the spilled substrate andremediation of the environment.

These changes in hydrophobicity (chemical) and in lattice (crystal) orsolid-phase structure (physical) of the material substances beingremediated, in the aqueous medium or bulk fluid, and in the compositematerial being removed (e.g., the oil-ice composite)—result in threeindependent methodologies or technologies for the clean-up of oil-spillsand other pollutant wastes:

-   -   a) viscous agglomeration;    -   b) accretion and encapsulation; and    -   c) sequestration by lattice uptake.

These three methodologies can be employed strategically, uponconsideration of the specific properties of the pollutant materials tobe remediated and/or the conditions of the operating environment. Thus,some implementations provide a choice of methodologies that are specificto a given substrate, or class of hydrophobic substrates, and/or toparticular spill conditions, and yield the capacity for increasedfacility in the sequestration, transport, and removal of such pollutantmaterials; thus providing, generally, for the easier and quickerclean-up of spilled oil and other immiscible substrates. Generallyspeaking, heavier weight oils are better suited to viscous agglomerationand accretion and encapsulation, whereas lighter oils are better suitedto sequestration by lattice uptake.

Put simply, viscous agglomeration refers to the increase in viscosityand density of the immiscible substrate upon application of thecondensed phase cryogenic fluid. The viscosity of the immisciblesubstrate increases to the point that it can be handled as or like asolid. This is due to the hydrophobic effect, where the immisciblesubstrate “balls-up” and repels the aqueous or hydrophilic bulk medium.Accretion and encapsulation, like viscous agglomeration, is based on thehydrophobic characteristics of the immiscible substrate—i.e., where uponapplication of CPCF, the immiscible substrate gathers together andthickens, or agglomerates, repelling the surrounding water or aqueousbulk medium, and producing a meniscus. Application of additional CPCFyields further cooling of the viscous agglomerate, and its accretion toan even denser (more compactified) substance. The meniscus thus appears,first, as the viscous agglomerate; which then, upon further applicationof CPCF, as it continues to accrete, becomes encapsulated within a massof solid water-ice as the temperature of the aqueous bulk medium isreduced (locally). With lighter weight oils and immiscibles, i.e., wherethe hydrophobic effects (and thus changes in viscosity) are lesspronounced, the oil or immiscible is encapsulated into the water-ice ina more liquid form (e.g., one can pick up a chunk of ice and observepockets of the encapsulated oil or immiscible that can freely flowwithin the specific pockets). The immiscible substrate can then behandled as a solid (ice-oil composite); in this case an encapsulatedproduct trapped in the solid lattice of the ice. While produced viaapplication of CPCF in a manner similar to that of the “solid” of thethick tar-like in the case of the viscous agglomerate, the encapsulationmethodology traps the oil or immiscible in regions of a bulk solid ofwater-ice (and remains more fluid or is accreted and becomes moreviscous, depending upon the properties of the immiscible (or type ofoil)); whereas in the agglomeration methodology there is no bulk ice andthe oil or immiscible (usually of a heavier weight or denser product)becomes sufficiently viscous or tar-like to be removed or remediateddirectly. Lattice uptake occurs, upon longer exposure to the CPCF, andcooling of the ice-oil mixed-state to a temperature of belowapproximately 100 degrees Kelvin (100 K or ≈−173° C.), and optimallywhen cooled to between ≈60 and 90 K (between ≈−213 and −183° C.), whenthe water ice undergoes a transition to an amorphous solid phase(referred to as “amorphous solid water” or “ASW”). Upon this transitionin the water-ice lattice, or solid-phase dynamics of the mixed-state,the immiscible substrate is absorbed or taken-up into the pores of theamorphous structure.

The physical chemistry and/or material science of the process describesthe cryogenically induced changes in the spilled oils, or otherimmiscible pollutant substrates; either in terms of induced hydrophobiceffects that result in the viscous agglomeration, or (upon furthercooling) the accretion and encapsulation of the immiscible pollutant.When additional CPCF is applied and the local temperature is reducedbelow the thermodynamic threshold at ca. 100 K or −173° C. (with theprecise transition temperature also determined by salinity, turbidity,detrital organic carbon concentrations, and other specific properties ofthe bulk medium at the spill site), physical and/or material changesoccur in the water-ice lattice and bulk medium; the resultingsolid-phase dynamics of the oil-ice mixed state, within the amorphouswater-ice structure, yield the sequestration of the spilled oil orimmiscible pollutant by the process of lattice-uptake.

The foregoing scientific principles are believed by the inventor to berelevant and are discussed in the interest of providing a completedisclosure. Those principles should not be taken as limiting theimplementations in any way.

FIG. 1 illustrates an implementation of a system 100 forenvironmentally-neutral remediation of oil-spill related contaminantsand the like. The system 100 may effect viscous agglomeration of thespill substrate, or its accretion and encapsulation, and/orsequestration via lattice uptake. The system includes a condensed phasecryogenic fluid source 101. The CPCF source 101 is, in someimplementations, one or more insulated vessels that are adapted tokeeping the contents in the liquid state along with a pump to controlthe pressure in the supply pipe 110. One example of an implementation ofa cryogenic fluid source 101 includes a Dewar jar or vacuum flask. Suchvessels are often used to store liquids which become gaseous at wellbelow ambient temperature, such as nitrogen. The leakage of heat intothe extremely cold interior of the vessel results in a slow“boiling-off” of the liquid so that a narrow unstoppered opening, or astoppered opening protected by a pressure relief valve, is necessary toprevent pressure from building up and shattering the flask. Theexcellent insulation of the Dewar flask results in a very slow “boil”and thus the contents remain liquid for a long time without the need forexpensive refrigeration equipment. The escaped liquid that boils off canbe captured, compressed (or otherwise cooled) and reintroduced into thevessel to reduce fluid loss.

The CPCF source 101 can contain, e.g., liquid nitrogen that was createdat an industrial site and later adapted for use with the system 100.Alternatively, the CPCF source 101 can store compressed ambient gas 102,e.g., liquefied atmospheric air. One manner of converting the air into acryogenic fluid is through the use of a multistage compressor or acascade liquefaction system. The term “multistage compressor” candesignates either a single compressor assembly with a plurality ofcompression stages (e.g., a multistage centrifugal compressor with acommon shaft) or a series of physically separate compressor assemblies(e.g., two or more single stage compressors operatively connected inseries, with the outlet of a first compressor feeding the suction inletof a downstream compressor).

A cascade liquefaction system uses a series of refrigeration loops, eachhaving a single refrigerant, to cool the natural gas stream tosuccessively lower temperatures. Some cascade systems generally work asfollows. The first refrigeration loop utilizes propane as therefrigerant to cool the gas to about −40° F., and to condense therefrigerant used in the second loop. The second refrigeration loop useseither ethane or ethylene as the refrigerant to cool the gas to about−120° F., and to condense the refrigerant used in the third loop. Thethird loop uses methane or nitrogen as the refrigerant to further cooland condense the gas. The major pieces of equipment in a cascade systemare the compressors (at least one compressor for each refrigerant), acooling water system or ambient air coolers, refrigerant accumulators,expansion valves, and numerous heat exhangers. In the interest of energyefficiency, many of the heat exchangers and other parts of therefrigeration loops may be grouped inside one or more cold boxes. Mobile(or portable) multistage compression and cascade liquefaction systemsare currently available from vendors of cryogenic systems.

A controller 104 is provided to, among other things, monitor the statusof the CPCF source 101. The controller 104 receives signals from thecryogenic fluid source 101 indicative of, e.g., temperature of thefluid, the rate of boil-off and/or other loss, the amount of fluidremaining, and the pressure. The controller 104 can take the form of aPC, a special purpose processor or a PLC (programmable logiccontroller). The controller 104 also controls the pump in the fluidsource 101 so as to vary the pressure in the supply pipe 110. In someimplementations, the preferred supply pipe 110 is vacuum insulated.

The valve assemblies 103 are coupled to the condensed phase cryogenicfluid source 101. The valves of 103 perform two functions: a)controlling the fluid phases, i.e. the pressures of the liquid and vaporphases of the CPCF; this assembly acts as a “keepfull,” release valvesfor the purging of vapor (gas) phases that are generated by the heatfrom friction incurred in the pumping or transport of CPCF through aninsulated supply pipe; and in some implementations, this component of103 may also contain a phase-separator; b) controlling the rate of flowof CPCF from its source to the low pressure applicator 105. In someimplementations, it is preferred that the controller 104 control thevalve 103 such that the rate of cryogenic fluid flow can be controlledbased on the conditions including the pressures of vapor and liquidphases, and/or the phase densities of the cryogenic fluid, the amount ofcryogenic fluid remaining in the source 101, and the properties of thesubstrate (monitored by sensor heads 106).

Sensor heads 106 installed under CPCF delivery system (e.g., drizzle barmanifolds and/or sparging arrays) and may also include IR sensors,optoacoustic sensors, or the like, to determine the spill/substratethickness, IR signatures (e.g., as FTIR or Raman spectra of molecularvibrations from each organic moiety) and/or other measurements that makethe constituents of the spill, and their concentration in the spillsubstrate identifiable (or show their absence). The properties, e.g.,thickness, densities, viscosities, and/or IR spectra of the spillcomponents, as well as the properties of the agglomerated and/orsolidified substrate (solid mixed-state) are determined and monitored.In some implementations the data and/or measurements are also sent fromthe sensors to the controller 104 to control the flow and/ordistribution of CPCF, operation and/or navigation, or other aspects ofthe remediation systems.

The sensor heads 106 may also include a GPS receiver that receivessignals from one or more satellites 120 for navigational purposes.

The low pressure applicator 105 can take many forms, but in someimplementations, is adapted to minimize fluctuations in pressure andflow rate, and to maintain an optimally constant pressure, at (or asclose as possible to) atmospheric pressure during applications. Theapplicator 105 may include sparger bars, drizzle bars, spray-bars, orarrays thereof. Possible applicators are discussed in greater detail inconnection with FIGS. 5-12. The line pressures for CPCF inflow and flowrate of cryogenic fluid from the applicator 105 can be controlled by thecontroller 104. The controller 104 can be set to a particular flow rateby a user, and can maintain that rate by controlling the pump in thefluid source 101 and/or valves or the like in the applicator 105.

Maintaining a small pressure drop during use of the applicator 105 helpsto keep the applied cryogenic fluid in a condensed phase. The pressureof the liquefied nitrogen (LN) or other cryogenic fluid, as well as theallowable variability in pressure (the pressure range), is kept to aminimum throughout all stages of the operation in most implementations.Several techniques can be employed to this end:

a) To ensure the flow of a saturated liquid phase of cryogenic fluid orLN to the applicator device 105, and to maximize the delivery acondensed phase to the spill site 107 (note that spill site/contaminant107 is not generally considered to be part of the system 100), the LNpressure at the point of emission from the fluid source 101 and withinthe supply pipe (or cryogenic flex conduit) 110 that carries thecryogenic fluid to the applicator 105, is controlled (e.g., bycontroller 104), so as to maintain the pressure between the source 101and the inlet pressure valve of the applicator 105 at preferably <50psi. The pressure of the LN can be controlled by controller 104 directlyat the source 101, and pumped to provide a constant LN influx or inletpressure to the applicator 105 of <50 psi (e.g., as measured at theinitial pressure control valve of the device). Depending on theimplementation, LN influx pressures in the range from about 35 to 50 psiare preferred, but can vary as a function of the dimensions of the lowpressure applicator 105 (e.g., the length and diameter of the applicatorbar(s), and/or the size and configuration of the array (or assembly) ofapplicator bars used (see FIG. ZOT).

b) Delivery of a condensed phase or saturated liquid by the applicator105 is further enhanced by the use of cryogenic “keepfulls” or pressurerelease valves (that are set to open at a particular predeterminedthreshold pressure) 111, at various points along the flow path, whicheffectively vent off excess pressure, along with any gas phase LN(evaporated liquid). The threshold pressure can be varied by thecontroller 104. Also, in the case that a dangerous level of pressurearises in the supply pipe 110, the controller 104 can cause the releasevalve 111 to open.

c) Pressure is reduced at the inlet pressure valve so that the outflowof LN into the applicator 105 (i.e., applicator inflow pressure) is atslightly above atmospheric pressure.

d) Pressure of the LN from the applicator 105 (i.e., the outflowpressure) onto the immiscible substrate of the spill is at aboutatmospheric pressure.

Since LN is kept at about −195° C. (or about −320° F.), with a criticaltemperature of about −148° C., it partially vaporizes, even whentraveling through a vacuum insulated hose (such as 110 used between thesource 101 and the applicator 105), and the longer the distance of thehose 110, the greater the losses to gas. In addition, this gas can addsignificant amounts of pressure within the hose(s) 110, or in theapplicator 105. This can create more of a two phase LN flow (liquid andvapor), and if no compensation mechanism is employed, then a large forceis easily induced when the LN escapes from the applicator onto thespilled oil 107. Such a force can easily build within the system 100 (asthe condensed phase expands to vapor), and the higher pressure LNexiting from the applicator 105 in the vapor phase can then readilydisperse the pollutant 107, pushing it away from the cooled area, andmaking the remediation process much harder and longer, and more costly.Moreover, the mere release of the LN vapor phase onto the spill-site(even though it may remain and exit the sparging unit at the sametemperature) generally cannot cryogenically induce the same physical andchemical effects.

With vapor phase LN, one may be able to attain some viscousagglomeration, making the oil contract and repel the water in its nexus(and this could possibly make some of the heavier types of oil, or thehigher molecular weight hydrocarbons, somewhat more manageable).However, the delivery and distribution of vapor phase LN is generallyunable to induce sufficient chemical change or hydrophobic effects for afull viscous agglomeration of the pollutant substrate (even with 90weight gear oils and other more viscous substances), and is neithergenerally able to induce sufficient and timely physical changes in thebulk medium, as needed for the rapid formation of a water-ice latticethat is sufficiently strong (thick) for the process of accretion andencapsulation. Moreover, vapor phase LN is not generally able to coolthe substrate sufficiently for its rapid transition to a solid phase,and/or to sufficiently cool any of the oil-water-ice mixed-states suchthat lattice uptake is not possible, even when the vapor phase LN wasdelivered in much larger amounts, and for longer periods of time. Forexample, using vapor phase LN is unable to cause any appreciable amountof accretion and encapsulation and/or lattice uptake.

Thus, the maintenance and delivery of a maximally condensed or saturatedliquid cryogenic fluid (e.g., in droplets approximately the size andrange of raindrops) is preferred in most implementations. To maximizethe flux and delivery of condensed liquid phase LN, a low pressureapplicator 105, vacuum insulated tubing 105, and/or “keepfulls” orpressure release valves 111 at or near the inflow valve of theapplicator 105 can be employed. Alternately, a phase separator, in lieuof the “keepfulls” 111 can be employed to maintain an optimal flow ofcondensed LN. In implementations in which phase separators are utilized,the gas phase nitrogen can be circulated into the gas supply 102 andconverted back into LN.

The low pressure applicator 105 applies the condensed phase LN to thespilled oil 107 (or other like spill). As discussed, this causes theproperties of the oil to change such that it becomes more easilyhandled. A collector 109 (examples of which are discussed in connectionwith FIGS. 13-20) captures the oil and removes it from the spill site.The captured oil is transferred into a storage area 108. The storagearea 108 may be adapted to maintain the temperature of the oil (oroil/ice) or allow it to increase. In implementations that allow the oil(or oil/ice) to increase in temperature, the storage area may have aseparator that allows the oil to separate from any water (e.g., ice)that was collected by the collector 109. The water may be returned tothe site after separation (e.g., after filtering or ensuring anappropriate level of purity). Moreover, the oil can then be stored inthe storage area 108 for subsequent refining or other use.

FIG. 2, which illustrates the saturation properties of nitrogen, isrelevant to understanding the importance—in most implementations—ofmaintaining a near constant final pressure, at or very close toatmospheric pressure in the applicator 105, with minimal pressurefluctuations in the system 100. In the illustration, the Y-axisrepresents pressure (in PSI) and the X-axis represents temperature (in °Celsius). The line 201 represents the saturation point of nitrogen as afunction of temperature and pressure. Above the line 201, nitrogen is ina liquid phase. Below the line 201, nitrogen is in a gas phase. Thus, ifthe temperature of nitrogen is maintained at about −195° C., it must bekept at a pressure of at least about 21 PSI to maintain the liquid stateor condensed phase. A higher pressure is preferred in someimplernentations. Thus, to keep nitrogen in the liquid state, thepressure drop in the system (e.g., system 100 of FIG. 1) should beminimized such that nitrogen is not taken to a temperature/pressurebelow line 201.

FIG. 3 illustrates an implementation of a cleanup and controlmethodology. Some implementations produce condensed phase cryogenicfluid, e.g., at the spill site. For those implementations, the firststep is to produce the CPCF (301). The CPCF in those implementations canbe liquefied air (“LA”). In other implementations, a cryogenic fluid isbrought to the spill site. In those implementations, liquid nitrogen canbe used. Next, the flow of CPCF is initiated (302). To maintain the lowtemperature of the cryogenic fluid, it is preferred, in mostimplementations, that it flow through insulated channels (e.g.,insulated pipe 110 of FIG. 1). The pressure and temperature of thecryogenic fluid are monitored and controlled in some implementationssuch that the fluid remains in a substantially condensed phase, from thepoint of storage to the point of being dispensed by the applicator(303).

Before the cryogenic fluid is applied to the spill, the properties ofthe spill e.g., thickness and densities, viscosities, molecularsignatures (or spectra) are detected (314). Also detected are theproperties of the agglomerate and/or solid mixed-state being removed(305). The thickness of the spill and other properties affects theremediation techniques, so data pertaining to properties of the spilland/or transformed substrate are stored in the operational database orparameters store 307. Depending upon the implementation, the “substrate”refers to the nature and composition or mixture of the spilledpollutant(s) (e.g., oil), along with the surface layer of the aquaticbody or terrestrial boundary layer being remediated, and ischaracterized by the properties (miscibility, thickness, type(s),concentration(s), molecular signatures (spectra), and other propertiesof the spill components, etc.), and the nature, composition, and/ormixture of the pollutant materials being removed from the spill (e.g.,the agglomerated immiscible substance or oil, and/or the solidifiedice-oil composite). For example, if oil or another immiscible substanceis spilled into a particular region of the Atlantic ocean, then thesubstrate is the immiscible/water or oil/water mixture proximate to thesurface being remediated, and the solid mixed-state (agglomerated oil orimmiscible, and/or the ice-oil or ice-immiscible composite) removed fromthat spill site. However, for purposes of detecting the properties ofthe spill (or spilled substances) and/or the remediant (the agglomerateor solid mixed-state being remediated), it should be understood that theproperties of the substrate proximate to a sensor (e.g., item 106 ofFIG. 1) are detected, and not necessarily those of entire oil-spill orall of the substrate being removed.

Next, the condensed phase cryogenic fluid is then applied to the spillsite (304), e.g., the oil spill. As the cryogenic fluid is being appliedto the spill site, the properties of the transformed substrate aredetected (305) and stored in parameters store 307.

Based on the detected properties, it is determined whether the oil hasagglomerated or solidified sufficiently (306). This determination isinformed by parameters 307. Since different oils (or lipids, or otherimmiscibles) become more easily handled at different temperatures,densities, and/or viscosities, in some implementations the desired orselected properties are changed and/or induced by an amount justsufficient to produce the most effective handling characteristics (e.g.,to induce the viscous agglomeration, accretion and encapsulation, and/orsequestration via lattice uptake). The parameters 307 can be stored in acontroller (e.g., item 104 of FIG. 1), and may contain thecharacteristics for a variety of oils, e.g., gear oil, motor oil, crudeoil, food oils, mineral oil, and other immiscible substances. Theparameters 307 include data regarding the thickness of the spill and themolecular identities (spectra), densities, and viscosities, of the spillcomponents and the solid mixed-state being removed, which may cause thecontroller (e.g., item 104 of FIG. 1) to apply a different amount (or agreater volumetric rate) of CPCF to the substrate, and/or to controlother aspects or operations of the remediation systems.

If the oil has cooled or changed its phase or state sufficiently, it iscollected (308). In most implementations, the collection is done in amanner that removes a maximum amount of pollutant (e.g., oil) andminimum amount of the bulk material (e.g., ocean water). The oil is thenstored (309), and may be subsequently processed or reserved for someother use (e.g., for resale).

If the oil has not cooled or changed in phase or state sufficiently, itis determined how much additional CPCF is to be delivered and/ordistributed onto the spill substrate (310). The determination isinformed by parameters 311, which may be stored in a controller (e.g.,item 104 of FIG. 1). Parameters 311 may take the form of a store that isseparate from or integrated with the store associated with parameters307. Depending on the nature of the substrate and the environment beingremediated, it may be desirable that it not reach below a certaintemperature, or that it be changed to an increased or decreased amount.For example, some substrates may be home to sensitive aquatic ecosystemsthat will be damaged by freezing or otherwise reducing the temperatureof the water below a particular threshold. If the substrate is notsufficiently cooled, solidified, or otherwise changed, the flow of CPCFcontinues or is increased (312), and the loop continues at block 305.Blocks 305 and/or 306 can determine whether to increase or maintainfluid flow based on whether the substrate is far from or near to thethreshold temperature, or other threshold properties.

If substrate is not cooled enough or is being cooled at a rate that isnot optimal, the fluid flow continues or is changed accordingly (313).Block 313 can determine whether to decrease or maintain CPCF flow basedon whether (and/or how far) the substrate is above, below, or if just atthe threshold value. In this implementation, the CPCF flow continueseven if the substrate has become sufficiently cold. Since in someimplementations the spill material (e.g., oil) is not collected until itreaches an appropriate temperature, density, and/or viscosity, thesubstrate may have to be further cooled, or cooled more than desired. Inother implementations in which the substrate is particularly sensitive,the step can be modified such that if the substrate reaches a specificor threshold value, the flow of CPCF is stopped.

The determining and/or controlling aspects of blocks 302-306, 308, 310,and 312-14 can be accomplished using a controller, e.g., item 104 ofFIG. 1.

Central Hub

FIG. 4 illustrates an implementation of a central hub 401 that may beused in conjunction with the remediation systems of FIGS. 1 and 13-20.This implementation of a central hub 401 is a barge-like vessel thatserves as: 1) a saturated liquid or condensed phase cryogenic fluid(CPCF) re-filling station and/or modular CPCP tank exchange point tore-supply CPCF and/or self-contained modular CPCF tanks to the mobiledelivery systems (see, e.g., FIGS. 1, 13-20); 2) a direct source of CPCF(e.g., condensed phases of liquid nitrogen, liquefied air, liquefiedcarbon dioxide, and/or liquefied inert gases) pumped to auxiliarycondensed phase delivery systems, e.g., tethered devices that act asapplicators delivering the CPCF onto the surface of the oil-spill; 3) acentral on-site container for storage of mixed phases of ice-water-oiland/or other remediated waste substrates pumped from the pollutant wastereceptacles, or intermediary storage tanks of the auxiliary and mobileCPCF delivery/pollutant-removal systems, and/or from the recycled wastestorage tanks of the modular remediation units; 4) a refueling site forsupply of diesel or other fuels, electric current, or for the exchangeof fuel cells, and/or recharging of electric storage batteries for themobile and auxiliary remediation systems; and 5) an on-site storagevessel for these modular CPCF tanks and modular oil-ice-water orpollutant waste receptacles, or intermediary storage tanks.

The hub 401 can be implemented in a variety of sizes, for example,10′×10′, 20′×20′, 40′×40′, or 100′×100′. Other sizes are possible toaccommodate the specific needs of particular users or spills. The hubcan be equipped with moorings spaced approximately 5 ft apart. Tanks 402and 403 are 2,500, 5,000 or 10,000 gal CPCF storage and refueling tanks.These tanks can be used for refueling (e.g., via pumped lines 416 or417) mobile remediation systems (e.g., those that have their own CPCFstorage tanks). In this implementation, pumped lines 416 or 417 are alsoused for filling the tanks 402 and 403. Tether lines 412 and 413 provideCPCF to auxiliary vessels or remediation systems (e.g., that includedrizzle bars and/or sparger units (or arrays) connected to tanks 402 or403) that remediate spills proximate to the hub 401.

Also, to provide quicker refueling of mobile remediation systems,modular CPCF delivery tanks or CPCF kegs 405 can be provided, which arepre-filled with CPCF. Tanks 405 may come in various sizes, with possiblesizes including 150, 250, 350 or 500 gallons.

In this implementation, storage tank 404 is a 10,000 or 20,000 gal tankfor storing immiscible- or oil-ice-water mixed phase and/or otherpollutants. Pumped lines 414 can be used for filing the tank 404 withthe waste collected by mobile remediation devices (e.g., those devicesthat have their own immiscible or oil-ice-water mixed-state storagetanks). The pumped lines 414 can also be used for discharging thecontents of the storage tank 404 for subsequent on-shore storage,recycling, purification, and/or sale. Tether lines 411 are used forfilling the tank 404 with the waste collected by the auxiliaryremediation devices (e.g., those devices that do not have their ownoil-ice-water mixed-phase storage tanks).

To allow mobile and/or auxiliary remediation devices to more quicklyempty collected pollutants, modular oil-ice-water or pollutant wastereceptacles 418 can be provided. A mobile or auxiliary device candispose a full receptacle 418 on the hub 401 and remove an emptyreceptacle 418 to quickly return to cleaning. The size of thereceptacles 418 can vary, but possible sizes include 250 and 500gallons.

The hub 401 also includes a communications and control center 420 whichprovides, e.g., global positioning (“GPS”) and navigational information,radio frequency (“RF”) infrared (“IR”) data (from sensors) andprocessing, and other mobile telecommunication capabilities. The controlcenter 420 can, in some implementations, transmit GPS data and operatinginstructions to the mobile remediation systems (see, e.g., FIGS. 1,13-20), e.g., for automated navigation of the remediation units aroundthe spill site. The control center 420 can also receive information frominfrared (IR) and/or optoacoustic sensors installed in the spargingunits of remediation apparatus to assess and/or monitor, in real time,the thickness of the spill (thus providing the means to estimate theremaining substrate volume to be remediated) and the temperature of thesubstrate. Moreover, the control center 420 can communicate informationand instructions to technical staff, field operations personnel,governmental authorities, etc.

A fuel tank 408 stores fuel. In some implementations, diesel fuel isutilized. The size can vary, but is 2500 gallons in this implementation.The fuel tank 408 provides fuel to a power supply 407 (e.g., agenerator) and a motor 410 that can be used for propelling the hub 401.In some implementations, the hub 401 is pulled by another device (e.g.,via tow-bar assemblies 409). The fuel tank 408 can fuel mobileremediation devices via pumped lines 415. Pumped lines 415 can also beused for refilling the fuel tank 408.

The power supply 407 is used for supplying electricity to, among otherthings, a CPCF condenser 406. In some implementations, the condenser 406is a cryogenic air and nitrogen liquefaction condenser and phaseseparator. The condenser 406 can condense ambient air to createliquefied air (LA) or can capture gaseous nitrogen and create liquefiednitrogen (LN). The LA or LN is stored in the tanks 402 and/or 403.

Implementations of Applicators for Applying CPCF

Prior to discussing particular implementations of remediation apparatus(and associated hardware), it is instructive to first discussimplementations of applicators that can be employed by such apparatus.While the following describes particular applicators in detail, itshould be understood that the actual applicator implemented with aparticular remediation apparatus can vary. For example, the shape andsize of the applicator may vary depending on the intended use of theremediation apparatus. An apparatus intended for remediating a largearea may be implemented with a large array of applicators (in a varietyof shapes and configurations), whereas a “hand-held” remediationapparatus may implemented with a small applicator.

As discussed above, it is a concern in some implementations that theapplicator cause as small of a pressure drop as possible to ensure thatthe cryogenic fluid remains in the condensed phase. Accordingly, thefollowing implementations of CPCF applicators are configured so as toresult in a small pressure drop, and thereby apply a CPCF to asubstrate. As a result, these applicators and the vessels and/orapparatus in which they are implemented may cause viscous agglomeration,accretion and encapsulation, and/or sequestration by lattice uptake ofan immiscible substrate.

FIG. 5 illustrates a view of an implementation of a sparger bar 500. Thesparger bar receives CPCF via an insulated hose 502. The hose 502,depending on the implementation, may be vacuum insulated. The generalconstruction of this implementation 500 includes of sparging regions 501and couplers 503. The sparging regions 501 dispense the CPCF(preferably, as close to atmospheric pressure as possible) whereas thecouplers 503 enable connection of additional sparging regions 501. Thus,the overall configuration of the sparger bar 500 can vary depending uponhow many sparging regions 501 and couplers 504 are utilized. End caps504 are used at the end(s) of the sparger bar 500 to ensure that CPCFescapes only through the sparging regions 501. In this implementation, alinear arrangement of couplers 503 and sparging regions 501 areemployed. Other implementations may employ a variety of shapes andconfigurations (e.g., circular, angular, etc.).

This particular implementation 500 may be implemented in connection witha hand-held remediation unit, and can be manually rotated, tilted,and/or aligned to different angles. Such a hand-held unit would havecapability, e.g., to be adjusted to the geometries of shorelines,coastal rocks, beach dunes, and/or to fit into tighter places such asunder and around piers or coastal flora.

The sparging regions 501 preferably distribute the cryogenic fluid indroplets. The sparging regions 501 are, in some implementations,fabricated by a sintering method. The sintered material can vary, butpossible materials include brass and bronze alloys, stainless steel,and/or silicon carbide (and composites thereof). In someimplementations, stainless steel and/or composite materials arepreferred, depending on, e.g., the properties, reactivity, and catalyticdegradability of the pollutant substrate to be remediated, thecharacteristics or severity of the spill and/or surrounding environment(e.g. using a particular composite material with greater porosity, inorder to distribute larger droplets over a spill area when wind orturbidity is significant, or to minimize the effects of seawater,brackish systems, and/or reactive or corrosive chemical spills) and theconditions of the marine/aquatic system (e.g., salinity, pH, solar fluxwithin the UVB band (280-320 nm) and aquatic concentrations of dissolvedorganic carbon (DOC) moieties or detrital matter (DOM) and theproduction rates for reactive oxygen species (e.g., transient oxidantssuch as OH, peroxyl, .O₂, hydroperoxyl, .O₂H, singlet oxygen,¹O₂(Δ_(g)), . . . ) and other free-radicals or degradation products).

The mean porosity of the different types of sintered metal suitable foruse as sparging regions 501 varies. For example, porosity may range fromless than 1 micron to over 10 microns. Yet, in some implementations, itmay be particularly preferred that porosity in the 2-3 micron range beemployed. Such porosities can be highly effective for the clean-up ofbulk crude oil, motor oils (10, 20, 30, and 50 W), motor oil blends andsynthetic “racing” oils (5-20, 10-30, 10-40, and 20-40W), vacuum pumpand gear oils (>90 W), mineral oils, vegetable oils (soy, corn, etc.)and/or other hydrophobic or immiscible substrates.

FIG. 6 depicts an alternate view of the sparger bar 500 for applyingCPCF.

FIG. 7 depicts an alternate implementation of a sparger bar 700. Thisimplementation is constructed in a manner similar to sparger bar 500 (ofFIG. 5), but employs only two sparging regions 701. The couplers 703 areterminated by end caps 704. The sparger bar 700 receives CPCF by way ofinsulated hose 702. This implementation may be implemented so that it issmaller than sparger bar 500 (of FIG. 5), thus making it applicable forhand-held operations that require a great deal of flexibility andprecision.

FIG. 8 is an alternate view of the sparger bar 700.

FIG. 9 depicts an implementation of another type of applicator, a spraybar 900. The spray bar 900 receives CPCF via an insulated (e.g., vacuuminsulated) hose 902. The CPCF travels through the bar sections 901 andis dispensed via nozzles 903. The nozzles 903 have adjustment dials 904which are used for adjusting the size of the nozzle 903 aperture. Putanother way, adjusting the dial 904 increases or decreases the size ofthe CPCF droplet that is dispensed, and/or the pressure of the CPCFflow. A coupler 905 can added to a bar section 901 to allow coupling ofadditional bar sections (e.g., a bar section 901 with additional nozzles903). End caps 906 are installed at the end(s) of the spray bar 900 toensure that CPCF is dispensed only through the nozzles 903. In thisimplementation, a linear arrangement of nozzles 903 and couplers 905 areemployed. Other implementations may employ a variety of shapes andconfigurations (e.g., circular, angular, etc.).

FIG. 10 is an alternate view of spray bar 900.

This particular implementation 900 may be implemented in connection witha hand-held remediation unit, and can be manually rotated, tilted,and/or aligned to different angles. Such a hand-held unit would havecapability, e.g., to be adjusted to the geometries of shorelines,coastal rocks, beach dunes, and/or to fit into tighter places such asunder and around piers or coastal flora.

The material of the spray bar 900 can vary, with possible materialsincluding stainless steel, non-reactive composites and/or specificpolymers, as required or preferred for particular implementations, ordepending on, e.g., the properties, reactivity, and catalyticdegradability of the pollutant substrate to be remediated, thecharacteristics or severity of the spill and/or surrounding environment(e.g. to minimize the effects of seawater, brackish systems, and/orreactive or corrosive chemical spills) and the conditions of themarine/aquatic system. Also, the materials and design concerns discussedin connection with implementation 500 are relevant to thisimplementation as well.

The geometry of the spray bar 900 can vary, but possible dimensionsinclude a bar section 901 diameter of about 0.75″ to about 1.5″. Theadjustable nozzles 903 can take many forms, but some implementations mayuse a pre-fabricated or adjustable cryogenic nozzle, e.g., as producedby Spraying Systems Co. of Wheaton, Ill.

FIG. 11 is an implementation of a drizzle bar 1100 for applying CPCF.The drizzle bar receives CPCF via an insulated (e.g., vacuum insulated)hose 1102. The CPCF travels through the bar sections 1101 and isdispensed through hole arrays 1103. A coupler 1105 can added to a barsection 1101 to allow coupling of additional bar sections (e.g., a barsection 1101 with additional hole arrays 1103). At the end(s) of thedrizzle bar 1100, end caps 1106 are installed to ensure that CPCF isdispensed only through the hole arrays 1103. In this implementation, alinear arrangement of bar sections 1101 and couplers 1105 are employed.Other implementations may employ a variety of shapes and configurations(e.g., circular, angular, etc.).

The hole arrays 1103 may include a sequential pattern of holes (e.g.,pentagons), with the bore of the holes being approximately from about0.1 mm to about 0.5 mm (though greater bores are possible for specificuses or applications). The bar sections 1101 may be fabricated inlengths of from about 1′ to 10′ or more, and diameters from about 1″ tomore than 5″.

This particular implementation 1100 may be implemented in connectionwith a hand-held remdiation unit, and can be manually rotated, tilted,and/or aligned to different angles. Such a hand-held unit would havecapability, e.g., to be adjusted to the geometries of shorelines,coastal rocks, beach dunes, and/or to fit into tighter places such asunder and around piers or coastal flora.

The material of the drizzle bar 1100 can vary, with possible materialsincluding stainless steel, non-reactive composites and/or specificpolymers, as required or preferred for particular implementations, ordepending on, e.g., the properties, reactivity, and catalyticdegradability of the pollutant substrate to be remediated, thecharacteristics or severity of the spill and/or surrounding environment(e.g. to minimize the effects of seawater, brackish systems, and/orreactive or corrosive chemical spills) and the conditions of themarine/aquatic system. Also, the materials and design concerns discussedin connection with implementation 500 are relevant to thisimplementation as well.

FIG. 12 is an implementation of an array of sparger bars 1200. Thesparger bars 1201, 1203 and 1204 can take the form the sparger barsdiscussed in connection with FIG. 5, and, accordingly, will not bediscussed in detail. The array 1200 receives CPCF via an insulated hose1201 (e.g., a vacuum insulted hose) and distributes the CPCF betweeneach sparger bar 1202, 1203 and 1204. Generally speaking, arrays can beuseful for applying CPCF to a larger area. The array can be made aslarge as needed, thereby allowing efficient application of CPCF to,e.g., a large oil spill. This array 1200 includes generally parallelsparger bars, but can take many forms. The array 1200 can includeconcentric circles, one or more spirals, or various other shapes orcombinations thereof. Generally speaking, arrays are not commonly usedwith hand-held remediation apparatus, and are instead better suited tolarger-scale apparatus.

Implementations of a Portable/Handheld Remediation Apparatus

The following implementations may be viewed as more particularimplementations of the system of FIG. 1 and/or the method of FIG. 3.Accordingly, the following may be read in view of, or in conjunctionwith, the discussion of FIG. 1 and/or FIG. 3.

FIG. 13 illustrates an implementation of portable/handheld remediationapparatus 1300. The apparatus 1300 may be used for the capture, removaland/or quarantine of hazardous materials (e.g., pollutants, noxiouschemicals, radioactive materials, etc.). The apparatus 1300 is suited toa wide variety of environments, ranging from confined spaces, indoorareas, airports, power plants, to hard/terrestrial surfaces, coastalrocks, to beaches, estuaries, or fragile ecosystems, to remote placessuch as mountain or wooded areas, streams, remote shorelines, deserts,bunkers, and/or use in war zones, catastrophic or emergency situations.

The apparatus 1300 as shown is implemented as a portable handheldremediation unit for, e.g., clean-up of both miscible and immisciblesubstrates from terrestrial areas and hard surfaces, generally. Thisapparatus 1300 can be operated from dune buggies,sport-utility-vehicles, pickup trucks, small boats, motorcycles,snowmobiles, and/or multi-terrain vehicles. One manner of implementingthe apparatus 1300 in conjunction with a vehicle is by mounting a lowpressure CPCF keg 1310 or other cryogenic fluid delivery system (e.g.,liquefaction system) and pollutant waste receptacle 1311 on suchvehicles. By using portable, back-packed, or self-contained(“scuba-like”) CPCF and waste storage tanks 1312, the apparatus 1300 maybe operated and implemented particularly for remediation and/or otherapplications in very remote locations, areas inaccessible even tooff-road vehicles, or where motor vehicles are not permitted, e.g.,marshes, streams, wildlife refuges, migratory wetlands, or other fragileor shallow-water ecosystems.

Generally speaking, the apparatus 1300 includes a handheld wand 1301, amulti-functional sparging unit 1317, plus a vacuum uptake system 1315 toremove pollutant waste in a one-step (or real time) process. Put anotherway, as the immiscible substrate 1319 is captured, it is vacuumed into awaste tank (e.g., 1311). The apparatus 1200 therefore is capable ofminimizing exposure times to hazardous spills (for the community as wellas for the remediators) by simultaneously capturing and removing thepollutant waste, and sealing the hazardous substance in a pressurizedreceptacle (or waste ‘keg’) 1311. Remediation, e.g., of buildings,coastal rocks, and/or other hardened or solid surfaces, can be furthersped up by employing rotating wire brushes (or brushes of non-reactivepolymeric or other materials). 1314 feeds the pollutant waste 1319 intothe vacuum uptake (1316 or 1313), so that the pollutants—whethercaptured as viscous agglomerate, as encapsulated substrate, and/or asthe mixed-state sequestered via lattice uptake—can be ‘quarantined’(sealed in the appropriate containers, e.g., 1311) as they are captured.This implementation is well suited for rapid response, emergencysituations in densely populated areas, and applications concerning smallhazardous spills of reactive chemicals, corrosives, or combustibles, forincendiaries, and/or in response to radiological or biological threats.

The wand shaft 1301 incorporates a CPCF delivery system (1317) and avacuum removal tool (1315). The upper section of the wand shaft 1301contains a cryogenic conduit for delivery of CPCF to capture thehazardous waste. The diameter of the conduit may vary, but diametersfrom about 0.5″ to about 3″ are preferred, with 1.5″ ideal in someimplementations. The lower section of the wand shaft 1301 contains avacuum tube (or flexible hose), lined in a non-reactive compositematerial, for removal of the waste substrate 1319. The diameter of thevacuum tube may vary, but diameters from 1.5″ to 5.5″ are preferred,with 3.5″ ideal in some implementations. The length of the wand shaftvaries, but lengths from 6′ to 18′ are preferred, with 12′ being idealin some implementations. This apparatus 1300 can be implemented in ahigher capacity format, thus requiring CPCF delivery at rates requiring5″ or greater diameter conduit and/or 6″ or greater diameter vacuumefflux tubing.

The CPCF sparger unit 1317 can take many forms, including thoseapplicators discussed in connection with, e.g., FIGS. 5-12. Inparticular, the sparger unit may take the form of a curved drizzlemanifold as described in connection with FIG. 12, an assembly or bundleof smaller diameter sintered metal sparger bars (e.g., such as FIG. 5 or7) fabricated into the exit end of a curved housing (made of stainlesssteel or non-reactive composite material), and/or as a spray bar (e.g.,such as FIG. 9) array or manifold, for delivery of low pressurecondensed droplets of CPCF 1318 onto the spill or site to be remediated1319. The sparger unit 1317 is adjustable in direction and in thedispersion pattern and area (e.g., in droplet size and density of CPCFper unit of spill surface area). The sparger unit 1317 is connected tothe cryogenic conduit for CPCF delivery, and couples to the CPCF influxpressure valve assembly and the control knob 1303 (discussed below).

A vacuum uptake system 1315 located near the surface of the spill 1319can provide vortex action for maximal suction and removal rate of thesubstrate to be remediated. The vacuum system 1315 connects directly toa vortex chamber and mechanical auger in which the solid phase isfragmented pneumatically (by vortex action) and mechanically (by theauger) and rapidly evacuated to the sealable waste receptacle (e.g.,1311). The vacuum system 1315 may include more than one inflow port, andis illustrated here with two (1313 and 1316). The inflow ports 1315,1316 may operate simultaneously or may be individually selected, e.g.,depending on the orientation of the wand 1301 relative to the spill1319. Alternatively, the suction can be continuously varied between thetwo inflow ports 1315, 1316. Control lever 1306 (which communicates vialinkage 1320) can be used to select the vacuum ports.

Rotating brushes 1314 of specific composition (e.g., wire brushes suchas stainless steel or brass, polyethylene for corrosive materials, ornon-reactive composites where required to deal with specific hazards orconditions) are provided on the distal end of the wand 1301. The brushes1314 enhance remediation on surfaces such as, e.g., coastal rocks. Thebrushes rotate on the brush control arm 1321 and can be raised, lowered,and positioned relative to the spill surface, via the brush control armlever 1304. The rotational speed of the brushes is controlled by thelever 1305. Levers 1304 and 1305 communicate with the brushes 1314and/or brush control arm 1321 via linkage 1320.

The wand 1301 includes two handles 1302 and 1309. Lower handle 1309includes a handgrip controller to throttle the rate of CPCF delivery anda safety release (e.g., an on-off toggle switch). Upper handle 1302includes a handgrip controller to throttle the suction (or rate ofvacuum uptake) of the hazardous material. A safety release (e.g., anon-off toggle switch) is also incorporated in the upper handle 1302.

A CPCF influx control knob (or pressure valve assembly) 1303 monitorsinflow from the CPCF delivery conduit 1315 (or the conduit associatedwith 1312) and adjusts the amount of CPCF pressure) flowing into thesparging manifold 1317.

The linkage 1320 is attached to top of the wand shaft 1301, and containsthe mechanical controllers associated with controls 1303, 1304, 1305 and1306. The linkage 1320 also contains the mechanical cables and circuitryfor the CPCF delivery and vacuum efflux throttles (and, e.g., on-offsafety switches) installed in the handles 1302 and 1309.

The CPCF keg 1310 is connected to the wand 1301 via a connecting hose1307, which preferably is insulated (e.g., vacuum insulated). The wastereceptacle 1311 is connected to the wand via a connecting hose 1308. Insome implementations (e.g., in cases in which the remediated pollutantis harmful or toxic) it is desirable to keep the waste frozen. In thatcase, it is preferred to use an insulated connecting hose 1308. Someimplementations may even utilize CPCF from keg 1310 or another source tokeep the waste inside the receptacle 1311 frozen. Similar hoses andconfigurations can be employed in connection with portable tank assembly1312. The keg 1310 may take a form analogous to, e.g., item 405 of FIG.4. The keg construction may take several forms, but in someimplementations is a modular, recyclable, CPCF Dewar jar. The keg 1310may come in a variety of sizes depending upon the implementation, e.g.,from 25 gallons up to 350 gallons or more. The keg 1310 may be re-filledor exchanged for replacement (full) kegs at the on-site central hub(e.g., of FIG. 4) or an on-shore CPCF tank.

The waste receptacle 1311 is preferably a sealable container, and maytake a form analogous to item 418 of FIG. 4. In some implementations,the waste receptacle 1311 is suited for quarantine and removal ofhazardous (e.g., nuclear or biological) waste. Such implementations arediscussed in connection with, e.g., FIG. 20. The waste receptacle 1311can be made in a variety of sizes depending upon the implementation,e.g., from 50 gallons up to 500 gallons or more. The waste receptacle1311 can be emptied or recycled/exchanged at the on-site central hub(e.g., of FIG. 4) or on-shore pollutant waste storage tank.

Some implementations of the wand 1301 can be used in conjunction withself-contained (“scuba-like”) CPCF delivery and pollutant waste tanks1312. Given that, in most implementations, these tanks are designed forportability, they may be provided in relatively small sizes. Possiblesizes include 10, 25, and 50 gallons per side (i.e., per CPCF tank andwaste tank). Note that the individual tanks of item 1312 need not be ofthe same capacity, e.g., a 10 gallon CPCF tank and a 50 gallon pollutantwaste tank. When a wand 1301 is used with the self-contained tanks 1312,tanks 1310 and 1311 may not be necessary. The small size of theself-contained tanks 1312 make the overall system, in someimplementations, particularly well-suited for remote and/or specializedapplications. For example, a self-contained implementation can beprovided in a backpack form (or otherwise transported) for use indoors,for densely wooded, estuarine, or otherwise unreachable environments,for remediation of fragile ecosystems, and/or for defense and securityapplications.

Implementations of Some Self-Contained Remediation Units

The following implementations may be viewed as more particularimplementations of the system of FIG. 1 and/or the method of FIG. 3.Accordingly, the following may be read in view of, or in conjunctionwith, the discussion of FIG. 1 and/or FIG. 3.

The CPCF sparger units discussed in connection with the followingimplementations can take many forms, including those applicatorsdiscussed in connection with, e.g., FIGS. 5-12. In particular, thesparger unit may take the form of a curved drizzle manifold as describedin connection with FIG. 12, an assembly or bundle of smaller diameterdrizzle bars (e.g., the sintered metal sparger bars in FIG. 5 or 7,and/or as spray bars such as FIG. 9) fabricated into the exit end of acurved housing (made of conventional materials, stainless steel, ornon-reactive composite material). These drizzle bars are employed inarrays, or manifolds, for delivery of low pressure condensed droplets ofCPCF onto the spill or site to be remediated. The sparger units may beadjustable in direction and in the dispersion pattern and area (e.g., toadjust CPCF droplet size and/or density, per unit of spill surfacearea). The sparger units may be connected to a cryogenic conduit forCPCF delivery, and may couple to CPCF influx pressure valves, phaseseparators, or other control assemblies that enable the adjustment ofCPCF flow and/or droplet properties according to the type of spilledmaterial(s), and/or according to the environment or conditions at thespill site.

FIGS. 14A and 14B depict an implementation of a self-containedremediation unit 1400. This implementation 1400 is generally disk-shapedand includes two major sets of components: (1) that which is generallyvisible at or above the surface of the substrate (FIG. 14A) and (2) thatwhich is generally not visible at or above the surface of the substrate(FIG. 14B). This implementation 1400 may find use in coastal andnon-coastal waters, and, given its generally circular design, cancollect waste in substantially all directions (e.g., over surfaces of360 degrees).

Starting with FIG. 14A, this implementation includes a deck 1420 thatstructurally supports two CPCF storage tanks 1413 and 1414. These tanksmay take the form of modular Dewars, or refillable containers and thelike. In some implementations, alternately, 1413 and 1414 may act asCPCF reservoirs in the active supply of CPCF (e.g., from a barge oranother vessel), and/or as components of supplemental CPCF flow systems.Also, 1413 and 1414 may be portable CPCF supply containers retrievedfrom (and/or recycled to) the hub of FIG. 4 (e.g., item 405). Someimplementations are adapted to be controlled by a human operatorsituated on the deck 1420. Such implementations include mechanicalassemblies or controls 1402 for directing the motion (steering andpropulsion) of the craft 1400, and/or for operation of the hydraulicand/or risers 1421. In other implementations, the craft 1400 is GPSnavigated and remotely controlled. Accordingly, GPS navigational controland antenna 1415 are provided. A roof/shield 1401 made of, e.g., alight-weight reflective material, is provided to protect the CPCFstorage tanks 1413 and 1414 and technical staff (e.g., when not operatedremotely via GPS), from direct effects of sunlight, wind, and/or waves.

The deck 1420 is supported by an array of pneumatic and/or hydraulicrisers 1421. These risers 1421 are coupled to the lower structure 1424of FIG. 14B, and control the height of the deck relative to thewater/substrate surface. Since the central waste tank 1422 (i.e., wherecollected oil/ice, spill waste products, and other materials beingremediated, are deposited and stored) is disposed near the deck 1420,adjusting the pneumatic and/or hydraulic risers 1421 adjusts the heightof the waste tank 1422 relative to the substrate surface. The pneumaticand/or hydraulic risers 1421 may be adjusted according to the prevalentwave height, overall turbidity, and/or wind conditions at the spill orremediation site. The central waste tank 1422 may be constructed invarious sizes, e.g., from less than 500 gallons to more than 25,000gallons.

Below the deck 1420 is a lower platform 1426 that may have approximatelythe same size and shape as the deck 1420. The lower platform 1426 neednot be extremely thick, but in some implementations, is fairly stiff andtough. Examples of appropriate materials include single- and multi-phasesteels, plastics, composites (e.g., incorporating carbon fiber and/orpolyamides) and aluminum alloys. Appropriate thicknesses and sizes varywith the implementations. For example, the lower platform may, dependingon the implementation, be between 0.5″ and 4″ thick. An apron 1417 iscoupled to the waste storage tank 1422 and/or lower platform 1426. Theapron 1417 can be made of a flexible low temperature polymer, or asynthetic rubber, or the like. It is attached to 1422 and/or 1426 alongonly its inner circumference, while the bulk apron is allowed to hangfreely, e.g., with the outer perimeter extending down into the watercolumn (below the surface of the spilled substrate). The upper surfaceof the apron 1417 generally defines a path, or 360° surface, from thesubstrate surface (spill) to the intake of central waste tank 1422.

Extending outwardly from the lower platform 1426 and/or deck 1420 areCPCF supply lines 1419 that are coupled to tanks 1413 and 1414 andslidibly coupled to the pneumatic lifters 1421. These supply lines 1419may take the form of insulated tubing (e.g., vacuum insulated) coupledto support rods. The supply lines 1419 are each connected to spargingunits (drizzle bars or manifolds) 1418 to provide the CPCF deliverysystems. The sparging units (drizzle bars or manifolds) can take manyforms, in order to preferably deliver CPCF to the surface of the spillsubstrate (e.g., according to spilled substrate or spill conditions).More particular examples of sparger configurations can be found in,e.g., FIGS. 5-12 and the description therewith. The spargers 1418 causethe substrate that is located at or near the terminus of the apron 1417to substantially increase in viscosity and to be cryogenically convertedvia viscous agglomeration, accretion and encapsulation, and/orsequestration via lattice uptake (e.g., to solidify), for efficacy ofremoval and/or remediation. In some implementation, each sparger unit(or drizzle bar manifold) includes a flotation device so that it remainsafloat and does not submerge into the water. Since the supply lines 1419are slidibly coupled to the pneumatic and/or hydraulic lifters 1421, thesparger units 1418 may move in the vertical direction. In someimplementations, the supply lines 1419 may only slide along the upperone-third of the pneumatic and/or hydraulic lifters.

Sensors 1404 (coupled to a controller, e.g., item 104 of FIG. 1) in someimplementations may be infrared (IR), near infrared (NIR), and/or oroptoacoustic (OA) detectors, to monitor, for example, the thickness andmakeup of the ice-oil composite or solid mixed-state (e.g., percent oilvs. water-ice, molecular properties, densities, viscosities, and/orrelative concentrations of different types of oil in the composite,),and/or for monitoring the thickness of the oil spill at a givenlocation, the relative concentrations, viscosities, molecular and/orother properties of the spilled oils (or other substrates orcontaminants). Thus, it can be determined, via monitoring the data fromthe sensors, the extent to which the substrate at or near the terminusof the apron 1417 has solidified, the concentrations (relative amounts,viscosities, and densities) and/or molecular composition of the ice-oilmixed-state, and such properties can be compared with those of theremaining oil or spill substrate. In this manner the efficiency of theclean-up operation (in terms of the composition of solid mixed-statebeing removed), as well as the rate and overall effectiveness of theremediation (in terms of the composition of the remaining substrate oroil spill) can be assessed and monitored. A data processor and antenna1416 can be used to transmit the raw data received from the sensors1406, and/or analyses of that data, to remote receivers (e.g., to acentral hub or remote communications center). The data from such sensorsmay also be sent (or fed back) to a controller, and used to control therate, droplet properties, and/or dispersal patterns over which CPCF isdelivered to the substrate, the operation of the control arms 1411,1409, 1408 and 1428 (e.g., the contraction/extension rates and/or forcesapplied by the hydraulic or pneumatic components), and/or to direct themotion of the vessel 1400.

The viscous agglomerate and/or solidified substrate (or solid ice-oilmixed-state) is collected and stored in the central waste tank 1422 bydragging the agglomerated or solidified substrate up along the apron1417 towards, and into, the tank 1422. Transport scoops 1406 aredisposed along the outside perimeter of the apron 1417, and coverapproximately 360 degrees. The transport scoops may be substantiallybasket-shaped and may have a perforated construction so that liquidsubstrate passes, while solid substrate is collected. The scoops 1406may be constructed of various materials, but should—in someimplementations—be fairly stiff and rigid, and resistant to lowtemperatures. Possible materials include single- and multi-phasestainless steel, aluminum alloys, polyethylene, silicon carbide orcarbon composite materials that are non-reactive (for use in spills ofcorrosive liquids, combustibles, and/or toxic/noxious or reactivechemicals).

The scoops 1406 are coupled to crossbars. The crossbars may supportbetween, e.g., 1 and 5 scoops. Visible from this perspective is crossbar1412 which supports two scoops; crossbar 1410 which supports fourscoops; crossbar 1407 which supports four scoops and crossbar 1405 whichsupports three scoops. Other crossbars are disposed on the opposite(far) side of the craft 1400 and are not visible in this perspective.Attached to each crossbar, respectively, is a control arm 1411, 1409,1408 and 1428. The crossbars and/or control arms, in someimplementations, are self-buoyant (e.g., rigid beams that are encased inbuoyant materials or have supplemental buoyant elements affixed) so thatthey are “free-floating” on one end (at the crossbeam), whileconstrained via attachment to small freely moving collars (or sleeveswith vertical degree of freedom) around the hydraulic or pneumaticlifters 1421. Thus, the scoops 1406, while tethered (with verticaldegree of freedom) at their inner end, can respond, automatically, tothe motion induced by wind and waves, and remain at (or very close to)the surface of the spill at their outer end. In some implementations,the control arms may slide only along the lower one-third of thehydraulic or pneumatic lifters 1421.

By controlling the control arms 1408, 1409, 1411 and 1428 (and in turnthe crossbars 1405, 1407, 1410, and 1412), the corresponding scoops 1406are caused to drag the agglomerated and/or solidified substrate (e.g.,the solid mixed-state of water-ice and oil or other spilled substance)inwardly towards and into the central waste tank 1422. The control armsmay be telescoping in some implementations. More particularly, thecontrol arms may be animated by hydraulic or pneumatic action, and maybe coupled to the supplies of the hydraulic or pneumatic risers 1421. Insome implementations, the dragging action is caused by drawing hydraulicfluid out of the control arms, causing them to shorten, while the actionof extension is caused by supply of hydraulic fluid into the controlarms. In some implementations, the scoops 1406 have a trapezoidalgeometry that allows them to pass freely under the sparger manifolds ordrizzle bars 1418.

FIG. 14B illustrates the lower part of the craft 1400. The lower partprovides, among other things, the foundation and support structure forthe operational components (associated with the upper part of FIG. 14A).It includes sponsons 1423 (e.g., adjustable pontoons), the cross-beamsand support structure 1424 (which may, in some implementations, containsupplemental floatation units) that provide buoyancy for the aspects ofthe system 1400, along with the power and propulsion units (e.g., adiesel powered jet boat drive 1425), and the adjustable hydraulic and/orpneumatic risers 1421 (also visible in FIG. 14A) that can independentlyraise and lower the deck 1420 and/or platform 1426 as needed (e.g.,according to the prevalent wave height and wind conditions at the spillsite). The jet boat drive 1425 may be powered by an on-board diesel fueltank 1427.

The size of the device 1400 can vary depending upon the implementation.Some implementations have a diameter of about 10 feet across, whileother implementations may be approximately 100 feet or more across.

FIG. 15 is an illustration of another implementation of a remediationunit 1500. This craft 1500 can be implemented for use in oil-spills andspills of other immiscible substrates, ranging fromsmall-to-large-scale, and can be used for open-ocean, coastal, inlandwaterway, and/or estuarine cleanup operations. The craft 1500 travelsgenerally in the direction of arrow 1550, collecting the substrate witha plow tip 1522, causing the substrate 1520 to flow under a spargerarray 1503 (which dispenses CPCF and causes it to increase in viscosityand/or solidify). The craft transports some of the agglomerated and/orsolid mixed-state of the spill substrate 1520 rearward toward a wastetank 1513.

Generally speaking, the craft 1500 includes three major sub-assemblies.The first sub assembly is the sled unit, which comprises sponsons (e.g.,adjustable buoyancy pontoons) 1502, sparger array 1503, sensor pack1519, plow tip 1522 and attachment rings 1504. In some implementations,there are two sponsons 1502, which are substantially parallel to eachother (this perspective hides the distant sponson from view, but it issubstantially similar to the near sponson). The two sponsons areseparated by a distance that varies with the implementation (e.g., fromabout less than three feet to more than 25 feet). That space between thesponsons 1502 is occupied by the sparger array 1503. The sparger array1503 includes, in some implementations, an array of sparging units ordrizzle bars (e.g., of FIG. 12) and a support structure to maintainrigidity of the array 1503. Accordingly, the substrate between thesponsons 1502 is exposed to CPCF from the sparger array 1503, whichcauses the substrate 1520 to become, e.g., a viscous agglomerate orsolid ice-oil mixed phase. Attachment rings 1504 can be used forattaching auxiliary capture devices (e.g., interchangeable plow tips1522). The attachment rings 1504 may also include adjustable buoyancydevices in order to adjust the sparger array depth relative to thesubstrate 1520 and maintain the most effective position of the plow tip1522 within the oil-spill boundary layer. The sensor pack 1519 performsfunctions similar to sensors 1404 of FIG. 14, and may be coupled to acontroller (e.g., item 104 of FIG. 1). The controller may be adapted tocontrol the rate of delivery of CPCF to the substrate.

The sled unit, in some implementations, is angled downward toward thesubstrate 1520 so the substrate 1520 is directed adjacent to the spargerarray 1503 and in the direction toward the waste tank 1513 (as the craft1500 travels in the direction of arrow 1550). The sparging units in thesparger array 1503 are adjustable so that the spargers may be configuredat different angles, and for a variety of CPCF dispersion patterns. Thesparger array receives CPCF from an on-board CPCF tank 1509 (e.g., aDewar, modular supply unit, or item 405 of FIG. 4) that is coupled toCPCF supply line 1521. The supply line 1521 is, in some implementations,vacuum insulated. The CPCF tank 1509 may come in various sizes dependingon the implementation, e.g., 150, 250, 350 or 500 gallons, and can bere-filled or exchanged for replacement (full) kegs at the on-sitecentral hub (e.g., of FIG. 4) or on-shore CPCF tank. The CPCF tank 1509is disposed in a housing 1525 that includes a pump, pressure controlvalves (e.g., keepfulls), a controller and insulated cryogenic conduitsand hoses (e.g., 1521) to transfer low pressure CPCF to the spargerarray 1503.

The second sub-assembly is the control section. The control sectionincludes controls for operating the craft 1507 (e.g., steering, speed,CPCF delivery rate, etc.), a roof 1508 to protect the operator, a seatfor the operator 1515, a deck 1518 that supports the structures thatmake up the control section, the CPCF tank 1509, the CPCF housing 1525and several waste and craft transport components. A compressor 1510 hasseveral functions. The compressor 1510 draws in the agglomerate and/orsolid mixed-state of the spill substrate (and some spill fluids pluswater) from one direction and discharges it at a higher pressure in asecond direction. The compressor 1510 can be diesel powered, forexample. A jet drive 1511 is coupled to the compressor 1510 (or directlyto a diesel power source) to provide motive force to the craft. Bydischarging the fluid rearward, the craft is able to travel forward.Also, the compressor is coupled to receive the substrate 1520 thatpasses under the sparger array 1503 and pass it through a vortex chamber1512, for eventual deposit in the waste tank 1513 via transport path1514. The compressor 1510 and vortex chamber 1512 cause mechanical andpneumatic fragmentation of the ice-oil solid phase by an auger, and viavortical action by compressed air. In other implementations, thecompressor is not used to transport the substrate 1520 into the wastetank 1513. Instead, a blower unit 1516 collects the incoming substrate1520 and projects it (1524) into the waste tank 1513. Implementationswith the blower unit 1516 preferably employ a waste tank 1513 with anopen top to allow the projected substrate (1524) to be depositedtherein.

The third sub-assembly is the waste section. It includes the waste tank1513, sponsons (e.g., adjustable buoyancy pontoons) 1501, attachmentrings 1505 and 1506, and lock bars 1517 that couple the waste section tothe control section. Attachment rings 1505 may further couple the wastesection to the control section, and also may provide additional buoyancycontrol. The waste tank 1513, in some implementations, is designed witha v-shape and efflux valves to additionally function as a separatoryfunnel-like container for separation of water and oil (or otherimmiscible substrate) phases.

The rings 1504 and 1505 are also usable for docking the unit at on-sitecentral hub (e.g., of FIG. 4) for servicing (re-fueling, re-filling orrecycling/exchange of CPCF kegs, transfer of remediated pollutantsubstrates to larger holding tanks, etc.), for towing the units, and/orfor loading/unloading or storing units on transport vessels.

As the craft moves in direction 1550, the spill site 1523 contains lessoil (or other substance being remediated) than substrate 1520.

While the size of the unit 1500 will vary depending on theimplementation, possible lengths include less than 12 feet to more than30 feet. In this implementation, the waste tank 1513 is shown to rightof the sparger array 1503. In other implementations, a secondary bargeor other type of storage vessel to contain and transport the retrievedproduct (e.g., cleaned-up oil-spill materials) from the spill site—orthe sparger array 1503 and related structure can be towed (e.g., by abarge, tug, or other vessel), and the frozen oil-spill material can beblown forward onto the towing barge (or onto a container onboard thetowing vessel).

FIG. 16A is an illustration of another implementation of a remediationunit 1600. This craft 1600 can be implemented for use in oil-spills andspills of other immiscible substrates, ranging fromsmall-to-large-scale, and can be used for open-ocean, coastal, inlandwaterway, and/or estuarine cleanup operations. In the exampleperspective that is illustrated, the craft 1600 travels generally in thedirection of arrow 1649, collecting the substrate 1620 with a plow tip1622, thereby causing the substrate 1620 to come atop a moving belt 1626and be cooled by a sparger array 1603 (causing it to increase inviscosity and/or solidify). The moving belt 1626 transports thecollected agglomerate and/or solid mixed-state of ice and spillsubstrate 1620 to a waste tank 1613.

Generally speaking, the craft 1600 includes three major sub-assemblies.The first sub assembly is the catamaran unit, which comprises sponsons(e.g., adjustable buoyancy pontoons) 1602, sparger array 1603, sensorpack 1619, plow tip 1622, belt 1626 and related pulleys (1627, 1628 and1629) and attachment rings 1604. In some implementations, there are twosponsons 1602, which are substantially parallel to each other (thisperspective hides the distant sponson from view, but it is substantiallysimilar to the near sponson). The two sponsons are separated by adistance that varies with the implementation (e.g., from about less than3 feet to more than 30 feet). That space between the sponsons 1602 isoccupied by the sparger array 1603, the belt (or conveyor) 1626 and itsrelated pulleys (1627, 1628 and 1629). The sparger array 1603 includes,in some implementations, an array of sparging units or drizzle barmanifolds (e.g., of FIG. 12) and a support structure to maintainrigidity of the array 1603. Accordingly, the substrate between thesponsons 1602 that is brought upon the belt 1626 is exposed to CPCF bythe sparger array 1603. This exposure causes the substrate 1620 tobecome, e.g., a viscous agglomerate or solid ice-oil mixed phase.

Attachment rings 1604 can be used for attaching auxiliary capturedevices (e.g., interchangeable plow tips 1622). The attachment rings1604 may also include adjustable buoyancy devices in order to adjust thesparger array depth relative to the substrate 1620 and maintain the mosteffective position of the plow tip 1622 within the oil-spill boundarylayer. The sensor pack 1619 performs functions similar to sensors 1404of FIG. 14, and may be coupled to a controller (e.g., item 104 of FIG.1). The controller may be adapted to control the rate of delivery ofCPCF to the substrate 1620.

The sled unit, in some implementations, is angled downward toward thesubstrate 1620 so the substrate 1620 is directed onto the belt 1626 andadjacent to the sparger array 1603. The sparging units in the spargerarray 1603 are adjustable so that the spargers may be configured atdifferent angles, and for a variety of CPCF dispersion patterns. Thesparger array receives CPCF from an on-board CPCF tank (e.g., a Dewar,modular keg, or item 405 of FIG. 4) that is inside the CPCF tank housing1625 and coupled to CPCF supply line 1621. The supply line 1621 is, insome implementations, vacuum insulated. The CPCF tank may come invarious sizes depending on the implementation, e.g., 150, 250, or 350gallons, and can be re-filled or exchanged for replacement (full) kegsat the on-site central hub (e.g., of FIG. 4) or on-shore CPCF tank. TheCPCF tank housing 1625 includes a pump, pressure control valves (e.g.,keepfulls or phase separator), a controller and insulated cryogenicconduits and hoses (e.g., 1621) to transfer low pressure CPCF to thesparger array 1603.

The belt 1626 is, in some implementations, made of a material that ishighly resistant to low temperatures (e.g., a polymer, synthetic rubber,or other conventional low temperature materials, as available fromvendors of cryogenic materials). In some implementations, the belt 1626is made of a metal mesh, such as stainless steel. A motor 1632 isdisposed opposite the CPCF tank housing and, in some implementations, incontrolled by the controller (e.g., item 104 of FIG. 1). Motor 1632causes the upper portion of the belt 1626 to travel toward the wastetank 1613 (naturally, the lower portion of the belt 1626 travels awayfrom the waste tank 1613). The belt 1626 is supported by a front pulley1627 near the plow tip 1622. In some implementations, front pulley 1627is a idler puller. Pulleys 1628 and 1629 (also idler pulleys in someimplementations) act as pinch rollers (or a capstan) and allow the belt1626 to incline upwardly relative to the sponsons 1602. Sincesubstantial portions of the top surface of the belt 1626 is carryingwaste material, the upper pulley 1629 preferably (in someimplementation) contacts a portion of the belt (e.g., the outermostportion(s)) that is not carrying waste material. The belt 1626 may havefeatures such as integral crossbars that prevent the solidifiedsubstrate 1620 from sliding downward as the belt 1626 inclines. Toprevent the solidified substrate from falling off the sides of the belt1626 as it inclines, side guides 1630 are disposed on both sides of theinclined section of the belt 1626. At the transition point of the belt'stravel (i.e., the point at which a given point on the belt stopstraveling toward the waste tank 1613 and beings traveling toward theplow tip 1622), the solidified substrate is ejected (1624) into thewaste tank 1613.

Some implementations utilize a hood 1631 over the catamaran section. Thehood 1631, among other things, takes advantage of mixed- and vapor-phasecryogenic fluid. Normally, as CPCF is applied to the substrate 1620,some CPCF is immediately transformed into the vapor phase, dispersesinto the atmosphere, and plays effectively no role in the remediationprocess. By installing the hood 1631 over the sparger array 1603, thevapor phase cryogenic fluid is kept near the substrate being remediatedand/or channeled over the path of the conveyor to assist in maintainingthe solid mixed-state and/or agglomerate. In some implementations, thehood 1631 is used to capture and recirculate the vapor phase cryogenicfluid. The hood 1631 may also increase user-friendliness by reducing anyimpairment in the region of vision for remediation staff and mobile unitoperators. In some implementations, hoods of specialized design andcomposition may be particularly important in operations involvingflammables, reactive chemicals, release/dispersion of radioactivematerials, and biohazards. More conventional retainers and hoods mayalso be advantageous in implementations for operations in warmer waterand/or at higher air or ground temperatures, as well rougher waters(e.g., to minimize effects of sea-spray and wave action), and foroperation in windy conditions

The second sub-assembly is the control section. The control sectionincludes controls for operating the craft 1607 (e.g., steering, speed,CPCF delivery rate, belt speed, etc.), a roof 1608 to protect theoperator, a deck 1618 that supports the structures that make up thecontrol section, the CPCF housing 1625 and several waste and crafttransport components. A compressor 1610 has several functions. Thecompressor 1610 draws in fluid from one direction and discharges it at ahigher pressure in a second direction. The compressor 1610 can be dieselpowered, for example. A jet drive 1611 is coupled to the compressor 1610to provide motive force to the craft. By discharging fluid rearward, thecraft 1600 is able to travel forward. Steering is accomplished byadjusting the direction of the jet drive 1611.

The third sub-assembly is the waste section. It includes the waste tank1613, sponsons (e.g., adjustable buoyancy pontoons) 1601, attachmentrings 1605 and 1606, and lock bars 1617 that couple the waste section tothe control section. Attachment rings 1606 may further couple the wastesection to the control section, and also may provide additional buoyancycontrol. The waste tank 1613, in some implementations, is designed witha v-shape and efflux valves to additionally function as a separatoryfunnel-like container for separation of water and oil (or otherimmiscible substrate) phases.

The rings 1604 and 1605 are also usable for docking the unit 1600 at anon-site central hub (e.g., of FIG. 4) for servicing (re-fueling,re-filling or recycling/exchange of CPCF kegs, transfer of remediatedpollutant substrates to larger holding tanks, etc.), for towing theunit, and/or for loading/unloading or storing units on transportvessels.

As the craft moves in the direction of arrow 1649, the substrate 1623contains less oil (or other substance being remediated) than substrate1620.

While the size of the unit 1600 will vary depending on theimplementation, possible lengths include less than 12 feet to more than30 feet. In this implementation, the waste tank 1613 is shown to rightof the sparger array 1603. In other implementations, a secondary bargeor other type of storage vessel to contain and transport the retrievedproduct (e.g., cleaned-up oil-spill materials) from the spill site—orthe sparger array 1603 and related structure can be towed (e.g., by abarge, tug, or other vessel), and the frozen oil-spill material can betransported forward on the belt 1626 onto the towing barge (or onto acontainer onboard the towing vessel).

FIG. 16B illustrates yet another implementation of a remediation unit1650, and is, in context, a variation of the implementation 1600 of FIG.16A. This craft 1650 can be implemented for use in oil-spills and spillsof other immiscible substrates, ranging from small-to-large-scale, andcan be used for open-ocean, coastal, inland waterway, and/or estuarinecleanup operations. In the example perspective that is illustrated, thecraft 1650 travels generally in the direction of arrow 1699, collectingthe substrate 1670 with a plow tip 1672, thereby causing the substrate1670 to come atop a moving belt 1676 and be cooled by a sparger array1653 (causing it to increase in viscosity and/or solidify). The movingbelt 1676 transports the collected agglomerate and/or solid mixed-stateof ice and oil immiscible substrate 1670 to a waste tank 1663.

Generally speaking, the craft 1650 includes three major sub-assemblies.The first sub assembly is the catamaran unit, which comprises sponsons(e.g., adjustable buoyancy pontoons) 1652, sparger array 1653, sensorpack 1669, plow tip 1672, belt 1626 and related pulleys (not visible inthis implementation, but similar to items 1627, 1628 and 1629 of FIG.16A) and attachment rings 1654. In some implementations, there are twosponsons 1652, which are substantially parallel to each other as shown.The two sponsons 1652 are separated by a distance that varies with theimplementation (e.g., from about less than 3 feet to more than 30 feet).That space between the sponsons 1652 is occupied by the sparger array(drizzle bar manifolds) 1653, the belt or conveyor 1676 and its relatedpulleys. The sparger array 1653 includes, in some implementations, anarray of sparger units or drizzle bars (e.g., of FIG. 12) and a supportstructure to maintain rigidity of the array 1653. Accordingly, thesubstrate between the sponsons 1652 that is brought upon the belt 1676is exposed to CPCF by the sparger array 1653. This exposure causes thesubstrate 1670 to become, e.g., a viscous agglomerate or solid ice-oilmixed phase. In this implementation, a sparger array 1653 can also belocated near the waste tank 1663. This maintains the substantiallyfrozen state of the substrate 1670, and is useful in applications, e.g.,for remediating heavy weight oils, flammable or combustible substrates,toxic, noxious, and/or hazardous substances.

Attachment rings 1654 can be used for attaching auxiliary capturedevices (e.g., interchangeable plow tips 1572). The attachment rings1654 may also include adjustable buoyancy devices in order to adjust thesparger array depth relative to the substrate 1670 and maintain the mosteffective position of the plow tip 1672 within the oil-spill boundarylayer. The sensor pack 1669 performs functions similar to sensors 1404of FIG. 14, and may be coupled to a controller (e.g., item 104 of FIG.1). The controller may be adapted to control the rate and/or pattern ofdelivery of CPCF to the substrate 1670, to operate the conveyors, and/orto direct motion of the vessel (when not operated in GPS mode).

The sled unit, in some implementations, is angled downward toward thesubstrate 1670 so the substrate 1670 is directed onto the belt 1676 andadjacent to the sparger array 1653. The sparging units in the spargerarray 1653 are adjustable so that the spargers may be configured atdifferent angles, and for a variety of CPCF dispersion patterns. Thesparger array receives CPCF from an on-board CPCF tank 1685 (e.g., aDewar, modular keg, or item 405 of FIG. 4) that is coupled to thehousing 1675 and CPCF supply line 1671. The supply line 1671 is, in someimplementations, vacuum insulated. The CPCF tank 1685 may come invarious sizes depending on the implementation, e.g., 150, 250, 350 or500 gallons, and can be re-filled or exchanged for replacement (full)kegs at the on-site central hub (e.g., of FIG. 4) or on-shore CPCF tank.The housing 1675 includes a conveyor drive assembly coupled to the belt1676, a pump, pressure control valves (e.g., keepfulls, phaseseparator), a controller and insulated cryogenic conduits and hoses(e.g., 1671) to transfer low pressure CPCF to the sparger array 1653.

The belt 1676 is, in some implementations, made of a material that ishighly resistant to low temperatures (e.g., a polymer, synthetic rubber,or other conventional low temperature materials, as available fromvendors of cryogenic materials). In some implementations, the belt 1676is made of a metal mesh, such as stainless steel. The conveyor driveinside the housing 1675 is, in some implementations, controlled by thecontroller (e.g., item 104 of FIG. 1). The conveyor drive causes theupper portion of the belt 1676 to travel toward the waste tank 1663(naturally, the lower portion of the belt 1676 travels away from thewaste tank 1663). The belt 1676 is offset to one side of the CPCF tank1685 and where the operator sits (i.e., adjacent the steering wheel andrelated controls 1657) so that it has a clear path into the waste tank1663. The belt 1676 may have features such as integral crossbars thatprevent the solidified substrate 1670 from sliding downward as the belt1676 inclines. At the transition point of the belt's travel (i.e., thepoint at which a given point on the belt stops traveling toward thewaste tank 1663 and beings traveling toward the plow tip 1672), thesolidified substrate is ejected (1674) into the waste tank 1663.

Some implementations utilize a hood 1681 over the catamaran section. Thehood 1681, among other things, takes advantage of mixed- and vapor-phasecryogenic fluid. As CPCF is applied to the substrate 1670, some CPCF isimmediately transformed into the vapor phase, disperses into theatmosphere, and plays effectively no role in the remediation process. Byinstalling the hood 1681 over a portion of the sparger array 1653, thevapor phase cryogenic fluid is kept near the substrate being remediatedand/or channeled over the path of the conveyor to assist in maintainingthe solid mixed-state and/or agglomerate. In some implementations, thehood 1681 is used to capture and recirculate the vapor phase cryogenicfluid. The hood 1681 may also increase user-fiiendliness by reducing anyimpairment in the region of vision for remediation staff and mobile unitoperators (when not operated in GPS mode). In some implementations,hoods of specialized design and composition may be particularlyimportant in operations involving flammables, reactive chemicals,release/dispersion of radioactive materials, and biohazards. Moreconventional retainers and hoods may also be advantageous inimplementations for operations in warmer water and/or at higher air orground temperatures, as well rougher waters (e.g., to minimize effectsof sea-spray and wave action), and for operation in windy conditions.

The second sub-assembly is the control section. Main components of thecontrol section include controls for operating the craft 1687 (e.g.,steering, speed, CPCF delivery rate, belt speed, etc.), a GPSnavigational system and antenna 1683, a roof 1658 to protect theoperator, a deck 1658 that supports the structures that make up thecontrol section, housing 1675, CPCF tank or modular CPCF keg 1685 andseveral waste and craft transport components 1668. Atop the roof 1658are an antenna 1683 for transmission/reception of GPS signals (e.g.,from a central hub like that of FIG. 4 or a land-based control center)and GPS navigational operating system, and a data processor and antenna1683 for transmission of infrared and/or optoacoustic data from sensorpack 1669. A windshield 1684 provides further protection to the driver(when operated manually, without GPS system).

Also, a compressor 1660 has several functions. The compressor 1660 drawsin fluid from one direction and discharges it at a higher pressure in asecond direction. The compressor 1660 can be diesel powered, forexample. A jet drive 1661 is coupled to the compressor 1660 (or directlyto a diesel power source) to provide motive force to the craft. Bydischarging fluid rearward, the craft 1660 is able to travel forward.Steering is accomplished by adjusting the direction of the jet drive1661 (either manually or remotely via GPS navigational system).

The third sub-assembly is the waste section. It includes the waste tank1663, sponsons (e.g., adjustable buoyancy pontoons) 1651, attachmentrings 1655 and 1656, and lock bars 1667 that couple the waste section tothe control section. Attachment rings 1656 may further couple the wastesection to the control section, and also may provide additional buoyancycontrol. The waste tank 1663, in some implementations, is designed witha v-shape and efflux valves to additionally function as a separatoryfunnel-like container for separation of water and oil (or otherimmiscible substrate) phases.

The rings 1654 and 1655 are also usable for docking the unit 1650 at anon-site central hub (e.g., of FIG. 4) for servicing (re-fueling,re-filling or recycling/exchange of CPCF kegs, transfer of remediatedpollutant substrates to larger holding tanks, etc.), for towing theunit, and/or for loading/unloading or storing units on transportvessels.

As the craft moves in the direction of arrow 1699, the substrate 1673contains less oil (or other substance being remediated) than substrate1670.

While the size of the unit 1650 will vary depending on theimplementation, possible lengths include less than 12 feet to more than30 feet. In this implementation, the waste tank 1663 is shown to rightof the sparger array 1653. In other implementations, a secondary bargeor other type of storage vessel to contain and transport the retrievedproduct (e.g., cleaned-up oil-spill materials) from the spill site—orthe sparger array 1653 and related structure can be towed (e.g., by abarge, tug, or other vessel), and the frozen oil-spill material can betransported forward on the belt 1676 onto the towing barge (or onto acontainer onboard the towing vessel).

FIG. 17 illustrates another implementation of a remediation vessel 1700.This vessel 1700 is modular in the sense that it can be configured forsmall jobs or expanded for larger jobs. Generally speaking, thisimplementation 1700 includes three major elements, namely, a controlsection (e.g., 1731), one or more auxiliary remediation sections (e.g.,1714), and a waste section (e.g., 1732). The auxiliary remediationsection 1714 is optional, e.g., for small jobs it may be omitted.Alternatively, larger jobs may utilize multiple auxiliary remediationsections 1714 in series as well as multiple waste sections 1732 inseries and/or (substantially) parallel.

The control section 1731 includes flying bridge 1729 at which the vessel1700 can be controlled (e.g., by personnel). Also, a GPS antenna andnavigation system 1703 and radio frequency broadcast system 1704 aredisposed in the flying bridge 1729. The GPS system 1703 allows remotecontrol and/or navigation of the craft 1700. The RF broadcast system1704 is for transmitting, e.g., data from infrared and optoacousticsensors affixed to the underside of each sparger array 1701, 1702, 1707,1708, 1715, and 1716 for monitoring the thickness of the immisciblesubstrate (e.g., indicating the progress of remediation) and thicknessof the solid/semi-solid remediated substrate (e.g., indicating theeffectiveness of the remediation operation), respectively.

Coupled to either side of the control section 1731 are sparger arraysand/or drizzle bar manifolds 1701, 1702, 1707 and 1708. These may takethe form of an array of sparger units or drizzle bars (e.g., of FIG.12). The sparger arrays receive CPCF from an on-board CPCF tank 1706.The tank 1706 may take the form of a Dewar, modular keg, and/or may beactively cooled. The tank 1706 may come in various sizes, such as 150,250, or 500 gallons. Alternatively, the tank 1706 may be a modular unit(e.g., item 405 of FIG. 4). The tank 1706 is coupled to the spargerarrays 1701, 1702, 1707 and 1708, thereby allowing the sparger arrays todeliver CPCF to the substrate. The application of CPCF causes thesubstrate to increase in viscosity and separate from the bulk fluide.g., as an agglomerate or a solid mixed-state (as shown, 1705). Thecontrol section 1731 is propelled by a jet boat drive 1711.

The auxiliary remediation section 1714 is coupled to the control section1731 by way of coupling arms (e.g., flex-bars) 1710. The auxiliaryremediation section 1714 carries its own CPCF tank 1717, which may takea form similar to tank 1706. Each auxiliary remediation section 1714 mayinclude its own CPCF tank, or tanks may be shared between auxiliaryremediation vessels and/or control sections. The CPCF tank 1717 iscoupled to sparger array 1715 and 1716 which may take substantially thesame form as sparger arrays 1701, 1702, 1707 and 1708. Each spargerarray may differ in size, shape and configuration. However, in mostimplementations, it is preferred that the sparger arrays deliver CPCF tothe substrate surface. The auxiliary remedation section is kept buoyantby sponsons (e.g., adjustable buoyancy pontoons) 1702 and 1703.

The auxiliary remediation section 1714 is coupled to the waste section1732 by coupling arms (e.g., flex-bars) 1730. The waste section collectsand stores the solid/semi-solid/mixed phase substrate 1705. As the craftproceeds (i.e., in direction 1735), guide screens 1718 and 1719 capturethe solid/semi-solid/mixed phase substrate 1705 and channel it ontoconveyor 1720. The conveyor 1720 transports the substrate 1705 into thewaste tank 1723. The waste tank 1723 may be modular (e.g., item 418 ofFIG. 4) and may also perform liquid-phase separation. Liquid phaserelease valves 1724, 1725 and 1726 may couple to a pump conduit forpurging pollutant waste efflux. These components are kept insubstantially operational alignment by a support structure 1727, whichin some implementations is made of a stiff material (e.g., single ormulti-phase stainless steel). Sponsons (e.g., adjustable buoyancypontoons) 1721 and 1722 support the waste section 1732. Due to theweight of the substrate that may accumulate in the waste tank 1723, thewaste section 1732 may have its own jet drive 1728.

For larger spills (or emergencies), one or more auxiliary remediationunits 1714 may be inserted and coupled (e.g., as middle sections)between the control section 1731 and waste section(s) 1732 in order toincrease the remediation rate, e.g., the surface area remediated perpass of the vessel 1700. Such multi-unit systems will also be employedto address the need for more rapid remediation in special applicationsand/or hazardous conditions, e.g., for spills of combustible materials,reactive chemicals, toxic/noxious wastes, or to reduce exposure of thepopulace to harmful materials released in (or associated with) cases ofchemical, biological, and/or radiological (nuclear) threats.

The size of the vessel and its sections will vary depending on theimplementation. For example, the control section 1731 may be designed asjet boats fabricated by modification of 16 foot or 21 foot catamaran and“trimaran” vessels, or as larger 30 foot or 40 foot barge-type vessels.Other sizes are possible, e.g., less than 16 feet up to more than 40feet. The size of the vessel may affect the size of the CPCF tank (e.g.1706). Modular (recyclable) 150, 250, or 350 gallon CPCF kegs may beinserted into housings into smaller vessels (e.g., 16 or 21 foot controlor auxiliary rernediation sections), whereas refillable 500-2,500 galloncryogenic supply tanks may be installed on larger vessels (e.g., 30 or40 foot barge-type control or auxiliary remediation sections).

FIGS. 18A and 18B depict two additional implementations of remediationvessels (1800 and 1850, respectively), which are particularlywell-suited for remediating heavier grade oils (e.g., gear oils andcrude oils).

FIG. 18A illustrates a first particular implementation of a GPSnavigated mobile remediation vessel 1800. The vessel 1800 includesseveral major components, including sparger array 1801 (see, e.g., FIG.12), a CPCF tank 1802 coupled to the array 1801 via CPCF piping 1822(which is insulated, e.g., vacuum insulated), a conveyor 1816, a wastetank 1803 and sleuth components (including 1804, 1808, 1810, 1811, 1812,1813 and 1814). The vessel 1800 is kept afloat by sponsons (e.g.,adjustable buoyancy pontoons) 1818. In this perspective only one sponsonis visible (i.e., the lee sponson), but in some implementations a secondsponson (i.e., a starboard sponson) is provided as well. The CPCF tank1802 may take many forms (e.g., a Dewar jar or akin to item 405 of FIG.4) and be a variety of sizes (e.g., less than 50 gallons to more than500 gallons).

The vessel 1800 may be unmanned and controlled remotely. A GPS antenna1806 receives and transmits GPS-related navigational data for directingthe craft. An RF receiver/transmitter 1807 transmits real-time data frominfrared and optoacoustic sensors 1805 installed under each spargermanifold 1801. The RF receiver/transmitter 1807 may also receive signalsthat relate to the delivery of CPCF (e.g., flow rate). Alternatively, acontroller (e.g., item 104 of FIG. 1) may receive data from the sensors1805 and automatically control the remediation operation. The controllermay be onboard the vessel 1800 or may be remote from it.

The sparger array 1801 delivers CPCF (shown as droplets 1819) onto thesubstrate 1820. This causes the substrate (e.g., an oil-water mixture)to increase in viscosity and become at least partially solid/semi-solid.The vessel 1800 travels substantially in the direction indicated byarrow 1824 due to, e.g., a diesel-powered jet drive 1817. Accordingly,front guide plates and ramps 1815 channel the substrate 1820 (which hasbecome, e.g., a viscous agglomerate or solid phase due to exposure toCPCF) onto the conveyor 1816. The conveyor 1816 can be either passive oractively cooled. In implementations that utilize an actively cooledconveyor, the conveyor 1816 is coupled to the CPCF tank 1802 anddispenses CPCF through the conveyor belt. This maintains the viscosityof the substrate 1820, and may induce farther phase changes (e.g.,viscous agglomeration to sequestration by lattice uptake). An activelycooled conveyor is discussed in greater detail in connection with FIG.18C. The conveyor 1826 includes a drive system to move the belt, and thebelt may be constructed of a metal mesh or some polymer or compositematerial capable of withstanding low temperatures (e.g., low temperaturematerials available from vendors of cryogenic supplies).

The conveyor 1816 carries the solid/semi-solid substrate 1820 toward thesleuth components. The material falls off of the conveyor 1816 and dropsinto the sleuth well 1814 (which is supported by sleuth platform 1813).Transport scoops 1808 (coupled to attachment cables) rotate about ashaft with a rotating cam 1811. As the scoops 1808 rotate, they capturematerial deposited in the sleuth well 1814 and transport it onto thestarboard conveyor 1812. The starboard conveyor 1812 may be activelycooled. Regardless, the starboard conveyor transports the material fromthe scoops 1808 into the waste tank 1803.

As a result, the substrate 1821 behind the vessel contains lesscontaminate than substrate 1820 ahead of the vessel.

FIG. 18B illustrates a second particular implementation of a GPSnavigated mobile remediation vessel 1850. The vessel 1850 includesseveral major components, including sparger array 1851 (see, e.g., FIG.12), a CPCF tank 1852 coupled to the array 1851 via CPCF piping 1872(which is insulated, e.g., vacuum insulated), a conveyor 1866, and wastetanks 1853A and 1853B (and associated conveyor 1854). The vessel 1850 iskept afloat by sponsons (e.g., adjustable buoyancy pontoons) 1868. Inthis perspective only one sponson is visible (i.e., the lee sponson),but in some implementations a second sponson (i.e., a starboard sponson)is provided as well. The CPCF tank 1852 may take many forms (e.g., aDewar jar or akin to item 405 of FIG. 4) and be a variety of sizes(e.g., less than 50 gallons to more than 500 gallons).

The vessel 1850 may be unmanned and controlled remotely. A GPS antenna1856 receives and transmits GPS-related navigational data for directingthe craft. An RF receiver/transmitter 1857 transmits real-time data frominfrared and optoacoustic sensors 1855 installed under each spargermanifold 1851. The RF receiver/transmitter 1857 may also receive signalsthat relate to the delivery of CPCF (e.g., flow rate). Alternatively, acontroller (e.g., item 104 of FIG. 1) may receive data from the sensors1855 and automatically control the remediation operation. The controllermay be onboard the vessel 1850 or may be remote from it.

The sparger array 1851 delivers CPCF (shown as droplets 1869) onto thesubstrate 1870. This causes the substrate (e.g., an oil-water mixture)to increase in viscosity and become at least partially solid/semi-solid.The vessel 1850 travels substantially in the direction indicated byarrow 1874 due to, e.g., a diesel-powered jet drive 1867. Accordingly,front guide plates and ramps 1865 channel the substrate 1870 (which hasbecome, e.g., a viscous agglomerate or solid phase due to exposure toCPCF) onto the conveyor 1866. The conveyor 1866 can be either passive oractively cooled. In implementations that utilize an actively cooledconveyor, the conveyor 1866 is coupled to the CPCF tank 1852 anddispenses CPCF through the conveyor belt. This maintains the viscosityof the substrate 1870, and may induce further phase changes (e.g.,sequestration by lattice uptake). An actively cooled conveyor isdiscussed in greater detail in connection with FIG. 18C. The conveyor1876 includes a drive system to move the belt, and the belt may beconstructed of a metal mesh or some polymer or composite materialcapable of withstanding low temperatures (e.g., low temperaturematerials available from vendors of cryogenic supplies).

The conveyor 1866 carries the solid/semi-solid substrate 1870 toward asecond conveyor 1854. Depending on the implementation, conveyor 1854 maybe actively cooled. Conveyor 1854 deposits the substrate 1870 intoprimary waste tank 1853A, which in some implementations is sufficientlywide to encompass the width of the conveyor 1866. As the primary wastetank 1853A fills, its contents are transferred to the secondary wastetank 1853B (e.g., gravitationally transported or pumped).

As a result, the substrate 1871 behind the vessel contains lesscontaminate than substrate 1870 ahead of the vessel.

FIG. 18C depicts a section 1875 of an actively cooled conveyor belt. Thebelt includes side members 1880 and 1881. In between the side members1880 and 1881 are at least two types of longitudinal members: coolingmembers 1876 and standard members 1877. The standard members are membersthat simply support what is being transported by the belt. The coolingmembers 1876 may take the form of or include CPCF dispensers 1878 (e.g.,sparger bars, drip bars, etc) that dispense droplets of CPCF upon thematerial transported by the belt. Accordingly, the transported materialis cooled as it travels on the belt.

Waste Tanks

FIGS. 19A-19D illustrate a rear view, front view, top view and sideview, respectively, of a waste tank 1900. Tank 1900, in various sizes,is adaptable for use with all of the foregoing remediation vessels andapparatus. The tank 1900 is a modular bi-modal waste receptacle forintermediary storage of pollutant substrate (e.g., oil-ice-watermixed-phase) and separation of the aqueous and immiscible pollutantsubstrate phases. These waste receptacles, which may be available invarious sizes, e.g., 500, 1,000, 2,500, or 5,000 gallons (volumetriccapacity), are modular. In other words, they can be recycled/exchangedfor empty replacement tanks (or directly emptied) at an on-site centralhub (e.g., of FIG. 4) or at an on-shore pollutant waste storage tank.Modular waste receptacles are designed with a ‘V’-shape and effluxvalves 1901 to additionally function as a separatory funnel-likecontainer for separation of water and oil (or other immisciblesubstrate) phases. Coupling bars 1902 are for attaching (or locking) thewaste tank 1900 to the vessel.

FIG. 20 illustrates a quarantine receptacle 2000 that may be used as aremediation device in and of itself, or may be used to quarantine a“dirty bomb” or terrorist device (e.g., item 1900) that is filled withCPCF to deactivate, contain, and/or sequester such devices or apparatus.The quarantine receptacle 2000 is constructed as a vacuum insulatedcontainer (e.g., that is steel, lead and composite layered), lined withnon-reactive material for the cryogenic deactivation, sequestration, andquarantine of harmful incendiary, reactive chemical, biological, and/orradiological devices. The receptacle is operated by remote control(e.g., via transceivers 2001) in order to increase safety of personnel,and to minimize exposure to and harmful or toxic materials. A fork liftunit (having wheels 2010) transports the receptacle 2000 to the item tobe quarantined. The receptacle 2000 is placed over a suspected harmfuldevice (e.g., a waste tank 1900), and as the receptacle body 2005 isfilled with CPCF (condensed liquid nitrogen or a liquefied inert gas,e.g., argon or helium) via CPCF lines 2012 which are coupled to CPCFcartridges 2002 located within the wheel lift assemblies 2003. Thebottom plate 2006, which has a tapered edge, augmented with a narrow“plow-like” blade, is slid under the suspected device and locked intoplace using hydraulic cylinder 2009. Upon filling the receptacle withCPCF, the top plate 2007 is lowered into place (via arms 2013 coupled tohydraulic cylinders 2014), and locked, to seal and quarantine thesuspected device. Bollide or ball-like wheels, or a tractor-tread unitor the like 2011 then drop down from assemblies 2004 and lock into placeto facilitate transport of the receptacle 2000. The bottom 2006 and topplates 2007 are contoured, or stepped (in the manner of a safe) toeffectively seal the unit 2000, and the entire process is operatedremotely in some implementations. Links (sensors) 2001 to the remotecontroller are located on the front of the container, and the fork-liftunit 2008 (which moves via driven fork lift wheels 2010). The wheels2001 are lowered automatically upon the locking of the top plate 2007into place, or via remote control. Quarantine receptacles 2000 may beproduced in a range of sizes and materials to deal with specific threatsand security applications.

Phase Transitions

FIG. 21 illustrates an example of a polluted substrate exposed to CPCF.In this example, the pollutant is oil. As shown, the substrate hastransitioned into various stages of viscous agglomeration (identified byarrows marked VA), accretion and encapsulation (identified by arrowsmarked AE), and sequestration by lattice uptake (identified by arrowsmarked SLU).

FIG. 22 illustrates examples of a polluted substrate transitioningthrough various stages (through slides 2201 through 2208) of viscousagglomeration, accretion and encapsulation, and sequestration by latticeuptake.

Other Applications

The delivery and distribution of condensed liquid-phase cryogenic fluidsvia the disclosed and related apparatus and methodology are alsoapplicable in emergency situations, and in events associated withextreme hazards and potentially catastrophic results to a givencommunity, or to the general populace. The prospective applications ofthis technology in the areas of national defense and homeland securityare various, e.g., its use as a functional component in strategicresponse plans that deal with specific cases of nuclear, chemical, andbiological threats. This disclosure provides the capacity to affordpotentially important and life-saving contributions in that regard. Forexample, liquid phase cryogens, e.g., condensed phases of liquefiednitrogen (LN), helium (LHe), argon (LAr), and other non-reactive orinert gases, can be used in emergency situations and potentiallycatastrophic circumstances, at the site of a hazardous spill of reactivechemicals, flammable or combustible liquids, and/or noxious or toxicwaste; additionally, condensed phase cryogenic fluids can be used inhomeland security operations to effect: a reduction in the rate ofdispersion of chemical, biological, or radioactive materials, areduction in the risk to personnel engaged in the dis-arming of devicesthat pose a nuclear, chemical, or biological threat, and a reduction inthe potential for detonation of such devices and/or release of thehazardous materials they may contain; to affect the cytolysis(lethality) and/or diminish the replication rate of hazardous biologicalagents (e.g., bacteria, viruses); as well as to reduce the reactivity ofharmful chemicals or chemically reactive agents, to lower the flashpointof a flammable substrate or explosive, for transient containment of anuclear device or radioactive materials (e.g., an un-detonated “dirtybomb”), and/or to remediate the products of such a chemical orbiological attack.

Environmental Impact

Some implementations are consistent with a new or higher standard ofenvironmental consciousness, i.e., one that: a) affects the environmentless and/or remains neutral or inert in its interactions with theenvironment; b) iterates a standard, defines the criteria forcompliance, and sets boundary conditions for environmentally-neutraltechnologies, processes for development, extraction of naturalresources, and operations relating to environmental clean-up andremediation; c) establishes clear and functionally viable protocols forenvironmentally-neutral technologies, along with goals and time framesfor discrete levels of attainment, and guidelines that enable andencourage compliance with such highly beneficial but more restrictivestandards.

Some implementations that rely on the use of CPCF are held to a standardof “environmental-neutrality,” and are described as being“environmentally-neutral” remediation systems—where“environmental-neutrality” relates to a standard for environmentalclean-up and remediation, and the term “environmentally-neutral” relatesto (or classifies) a technology or remediation operation that neitheremploys as an active agent in any clean-up process or remediationoperation, nor transports to the spill site or remediation environmentfor use as such an active agent, any material that is not natural or“normal” to (e.g., normally found in), and/or already present in thatenvironment or ecosystem. “Environmental-neutrality” can provide a clearand measurable basis for accurately describing the class of all“environmentally-neutral” technologies, and/or to quantify precisely thedegree of compliance or level of environmental-neutrality attained. Inaddition to its determinable property of neutrality (or inertness) andits high level of environmental-consciousness, it is this ability toquantitatively assess and evaluate a given technology or process,precisely, in terms of the absence of its interaction with theenvironment (neutrality) or the lack thereof, that distinguishes anddifferentiates some implementations from those conventionally describedas being “environmentally-friendly,” or those that maintain a sufficientlevel of environmental consciousness to be referred to as being “green(or blue) technologies.”

Other criteria often cited regarding environmental clean-up andremediation operations, e.g., in the environmental literature, byregulatory agencies, and/or in protocols for technological processes,per se, include “sustainability” and the goals (and suggestedguidelines) for “sustainable development.” “Environmentalsustainability” relates to the ability of the environment to continue tofunction properly indefinitely. The term “sustainable development”relates to a standard which, as defined by the United Nations BrundtlandCommission (1987, led by the former Norwegian Prime Minister Gro HarlemBrundtland) and promulgated by the U.N. Division for SustainableDevelopment (UN-DESA, 2007), additionally includes social and economicconcerns, and promotes development that “meets the needs of the presentwithout compromising the ability of future generations to meet their ownneeds.”

Some implementations may signal a new state-of-the-art in environmentalremediation, as those implementations that employ CPCF as the activeagent in an environmental clean-up or remediation process areenvironmentally-neutral, and are orders of magnitude faster and moreeffective than other remediation methods. Such implementations are alsoconsistent with (and/or incorporate) the principles and criteria of“environmental sustainability” since these CPCF based implementationsand applications act to minimize environmental degradation due to spillsof oil and/or other pollutants or toxic/noxious wastes. Theseimplementations may employ CPCF to capture and remove these spilledsubstrates and their degradation products, and the resultantenvironmentally-neutral remediation acts to halt/reverse the degradationprocesses at that spill site.

With particular regard to some implementations' production and use ofCPCFs, liquefied air or LN are environmentally-neutral and are neitherxenotrophs (e.g., substances foreign to, or not naturally found in, thegiven environment), nor have any polluting or contaminating long- orshort-term impact on the environment, nor yield any negative residualeffect(s). This is because, for example, nitrogen comprises about 78% ofair, on average, with oxygen about 21%, and the total of argon, carbondioxide, helium, NOx, SOx, etc., being <1%. Moreover, the liqueficationand/or production of CPCF is temporary and, e.g., subsequent to its useas active agent in the cryogenically induced remediation processes, theCPCF evaporates, and is naturally returned to the environment in itsambient gas (or vapor) state, while leaving the remediated substrate (orpollutant waste) contained and stored in a condensed state (solid and/orliquid).

Efficiency Compared with Other Approaches

The following is a brief overview of the efficiency of an implementationof a remediation approach that utilizes CPCF (i.e., consistent with thedisclosure herein) as compared to other approaches that do not utilizeCPCF.

Efficiency of the Exxon Valdez Cleanup Utilizing Non-CPCF Remediation

The Exxon Valdez left the Alyeska Pipeline Terminal at 9:12 p.m., AlaskaStandard Time, on Mar. 23, 1989. The 987 ft ship was loaded with53,094,510 gallons (1,264,155 barrels) of North Slope crude oil boundfor Long Beach, Calif. Less than three hours later, the Exxon Valdezcollided and was grounded at Bligh Reef, rupturing 8 of its 11 cargotanks, some 10.8 million gallons of crude oil were spewing into PrinceWilliam Sound. Computations aboard the Exxon Valdez showed that 5.8million gallons had gushed from the tanker in the first 3¼ hours.Weather conditions at the site were reported as being at a temperatureof 33° F., with slight drizzle of mixed rain/snow, north winds at 10knots, and a visibility 10 miles at the time of the grounding. Thewaters of Prince William Sound, and eventually more than 1,000 miles ofbeach in Southcentral Alaska, would be fouled by a spill of 10.8 milliongallons of crude oil. Three years after the spill, in 1992, the CoastGuard declared the cleanup complete. While, to this day, some claimthere are still observable quantities of oil in the effected area, andwhile many environmental problems remain, and wildlife are stillrecovering from this disaster, assume, arguendo, for the purpose ofcomputing a rough estimate of the clean-up and remediation efficiency ofthe spill, that the total 10.8 million gallons was remediated in thestated 3 years. Also assume for the purpose of this estimate, that theremediation operation was running 7 days per week and averaged 10hours/day over this period (ignoring seasonal variabilities in daylightworking hours and the effects of the Alaskan weather). Published reportsindicate that the total workforce consisted of about 11,000 Alaskanresidents, along with Exxon employees, and private contractors broughtin to assist in the clean-up operation. Thus, it can be very roughlyestimated that:

Thus (by assumption 1):

-   -   Total Remediation Time=10 hr/day×365 day/yr×3 yr=10,950 hr and    -   10.8×10⁶ (or 10.8 million) gal÷10,950 hr=986 gal/hr or    -   10.8×10⁶ gal÷42 gal/bbl÷10,950 hr=23.48 bbl/hr

If it is assumed that this total workforce was actively performingduties in the clean-up of the oil-spill at any given time, then theaverage hourly rate, or amount of oil removed per hour by each workeris:

-   -   986 gal/hr÷11,000 workers=0.0896 or ≈0.1 gal/hr/worker=2.38×10⁻³        bbl/hr/worker

If it is assumed (at the other extreme) that only about 1 out of every10 workers (or 1/10^(th) of this workforce) was working at any giventime, then the average hourly rate per worker for the clean-up of theExxon Valdes spill as:

-   -   986 gal/hr÷1,100 workers=0.896 or ≈1 gal/hr/worker=2.38×10⁻²        bbl/hr/worker

Efficiency of the Puget Sound Cleanup Utilizing Non-CPCF Remediation

In October 2004, more than 1,000 gallons of crude oil was spilled intothe Dalco Passage of the Puget Sound, a channel between Tacoma andVason, Wash., from a (then) unknown source. In December 2004, oil sampletests, independently conducted by both state and federal laboratories,indicated that a Polar Texas oil tanker, owned by Conoco-Phillips, wasthe source of the spilled oil that soiled beaches around Dalco Passage.The cleanup costs drew, inter alia, upon nearly $2 million from federaland state oil spill contingency finds. Countering claims that thatremediation of the spill had been completed effectively, in a Dec. 23,2004 press release, Rear Admiral Jeffrey Garrett of the U.S. Coast Guard(USCG) indicated that there was “more work to do” before determining theactual cleanup rate, the overall effectiveness of the remediationeffort, and “what enforcement action, if any, to take.” Cleanupoperations extended through January 2005 (without any clear consensus asto its actual completion or the criteria for determination of itssuccess). For purposes of this analysis, in order to minimize the timefor remediation of this oil spill, consider only the earliest claims forcompletion of the clean-up: the dates of Dec. 23, 2004, and Jan. 15,2005. Thus, here consider that ≦1,000 gallons of oil (and oil-watermixtures) was been cleaned-up in a time period estimated as being either84 or about 116 days. Assume that cleanup and remediation effortsproceeded on a daily basis, and an average of 8-10 hours/day.

Thus, for the October 2004, Dalco Passage (Conoco-Phillips) spill, wherethe source of ≈1,000 gallons of spilled crude oil impacted the PugetSound, Dalco Passage, and coastline (coastal rocks and beaches) in theTacoma and Vason, Wash. area, from the USCG and EPA databases (see,e.g., www.epa.gov/oilspill/pdfs/0107update.pdf) the most and leastfavorable estimates for the remediation times and efficiencies of ≈1,000gal of crude oil, degradation products, and water-oil mixtures,respectively, in ≈84 or ≈116 days (normalized to 8 hr/day actualclean-up work schedule) as follows:

Maximum Efficiency:

-   -   1,000 gal oil÷84 days=11.905 gal/day (i.e. per daily work        period)

→1,000 gal oil÷8 hr/day×84 days=1.488 gal/hr (average)

or considering 10 hr/day work periods:

-   -   1,000 gal oil÷10 hr/day×84 days=1.19 gal/hr (average)

Alternately, taking the clean-up period 116 days (assuming likewise 8-10hr/day work periods)

Minimum efficiency estimates for the remediation of 1,000 gal of oilare:

-   -   1,000 gal oil÷116 days=8.62 gal/day (i.e. per daily period)

→1,000 gal oil÷8 hr/day×116 days=1.078 gal/hr

or considering 10 hr/day work periods:

1,000 gal oil÷10 hr/day×116 days=0.86 gal/hr

Efficiency of a CPCF-based Cleanup Apparatus

It is instructive to compare the clean-up rates estimated above for thecase of the 1989 Exxon-Valdes spill and from USCG and the EPA findingsin the case of the October 2004 Puget Sound spill, with those clean-upand/or remediation rates for crude oil, computed bycomputational/analytic testing (“testing”) of CPCF-based remediationapparatus. Measurements and data as to clean-up rates (e.g., for crudeand processed oils, and other non-polar or immiscible chemicals andpollutants) and remediation efficiencies are determined in terms of thetimes required for remediation of ≧99% of the spill substrate. Thistesting further considered other criteria, including the monitoring ofwater quality issues, e.g., attaining potable water quality subsequentto remediation, and maintaining a standard of“environmental-neutrality.” Analyses were also conducted for assessmentof ratios of oil-to-ice-to-water for each type of oil or otherimmiscible substrate tested. Additional concerns include measurementsbased on initial spill, water, and environmental conditions, e.g., airvs. water temperatures, relative viscosities and molecular compositionof the spilled substrates, presence of volatiles,flammables/combustibles, reactive chemicals, and biological materials(non-harmful protists, algal cells, etc.), as well as with case-specificmaterials for use in applications (e.g., stainless steel, alloys,silicon carbide, polyethylene and other polymers, composites, etc.) andthe composition of the CPCF (e.g., liquefied air, liquefied nitrogen orhelium or argon, etc.) to be used for specific applications incryogenically inducing the state(s) of viscous agglomeration, accretionand encapsulation, and/or sequestration via lattice uptake.

Testing considers a range of marine and freshwater samples (e.g.,varying in turbidity, salinity, pH, detrital organic matter (DOM, DOC),algal, phyto- and zooplankton population dynamics), and includingsamples from seawaters, brackish and estuarine systems, rivers, lakes,streams and tributaries, tap, well, and distilled waters, tested overtemperatures ranging from 0-45° C., and pressures from ≈0.5-3 bar.However the variation in such properties does not, in most cases,substantial alter mean values.

Testing was performed, e.g., using a simple handheld sparging system (anexample of one type of a handheld sparging system is illustrated in FIG.13), under conditions that are most consistent with (or least dissimilarto) the properties of the spilled oil, and where comparative data is themean value (or average) computed from a minimum of 3 runs in cleaning-upor remediating the same (or highly similar) type of oil (or othersubstrate) in order to assure a valid and accurate basis for comparisonwith those rates, efficiencies, and/or results published or otherwisepromulgated as pertaining to such past spills. As in the case of PugetSound (Dalco Passage) crude oil spill, testing was normalized to 8-10 hrwork periods, and generated results and/or ranges of:

-   -   For crude oil #1, #2, and motor oils 5, 10, 20, 30W, and 5-20W,        10-30W blends

Class-1, Average Remediation Rate: ≈27.86 gal/hr/worker

-   -   →27.86 gal/hr/worker×8 hr/day=222.88 gal/day/worker    -   For crude oil #3, 50W, 20-50W motor oil, ≧90W gear, hydraulic,        vacuum pump oils

Class-2, Average Remediation Rate Range: ≈19.84-22.78 gal/hr/worker

-   -   →19.84 gal/hr/worker×8 hr/day=158.72 gal/day/worker    -   →22.78 gal/hr/worker×8 hr/day=182.24 gal/day/worker    -   For processed vegetable oils (soybean, corn, olive, safflower)

Class-3, Average Remediation Rate Range: ≈17.22-23.63 gal/hr/worker

-   -   →17.22 gal/hr/worker×8 hr/day=137.76-189.04 gal/day/worker    -   →23.63 gal/hr/worker×8 hr/day=137.76-189.04 gal/day/worker    -   For processed mineral oils

Class-4, Average Remediation Rate: ≈25.03 gal/hr/worker

-   -   →25.03 gal/hr/worker×8 hr/day=200.24 gal/day/worker    -   For synthetic “racing” oils with high performance over high/low        temperature/viscosity ranges

Class-5, Average Remediation Rate: ≈8.5 gal/hr/worker

-   -   →8.5 gal/hr/worker×8 hr/day=68 gal/day/worker

Thus, the performance of CPCF based technology in comparison with theExxon-Valdes clean-up operation shows, respectively, for the fullworkforce (>11,000, as declared) and for 1/10^(th) of the workforce(1,100), averaging 8-10 hr/day work periods:

Exxon Average: ≈0.1 gal/hr/worker (1,100 workers)

-   -   →0.1 gal/hr/worker×8 hr/day=0.8 or <1 gal/day/worker    -   →0.1 gal/hr/worker×10 hr/day=1 gal/day/worker

ExxonAverage: 0.896 or ≈1 gal/hr/worker (11,000 workers)

-   -   →0.896 gal/hr/worker×8 hr/day=7.2 gal/day/worker    -   →0.896 gal/hr/worker×10 hr/day=8.96 or ≈9 gal/day/worker vs.

CPCF Method—Average rate for clean-up and remediation of crude oil #1,and/or #2:

-   -   ≈27.86 gal/hr/worker→≈222.88 gal/day/worker

or comparatively the CPCF technology shows capacity for out-performingthe Exxon-Valdes clean-up rate by:

-   -   222.88 gal/day/worker÷1 gal/day/worker=222.88× or 22,288%    -   222.88 gal/day/worker÷7.2 gal/day/worker=30.95× or 3,095%    -   222.88 gal/day/worker÷8.96 gal/day/worker=24.875× or 2,487%

Therefore, crediting the Exxon-Valdes clean-up with operating 365days/year and 8-10 hr/day, the CPCF technology, using, e.g., a handhelddevice with a single 8 inch long CPCF sparging unit, shows the capacityfor out-performing the Exxon-Valdes method at a rate of over 222 timesfaster (if Exxon's full workforce was operating daily), and byapproximately 25-30 times faster (if only 1/10^(th) of Exxon's fullworkforce was operating daily) and with a relative efficiency increase(performance advantage) in the CPCF technology of:

-   -   (222.88 gal/day/worker−1 gal/day/worker)÷1        gal/day/worker=221.88× or 22,188%    -   (222.88 gal/day/worker−7.2 gal/day/worker)÷7.2        gal/day/worker=29.95× or 2,995%    -   (222.88 gal/day/worker−8.96 gal/day/worker)÷8.96        gal/day/worker=23.875× or 2,387%

Next, the performance of CPCF based technology in comparison with theclean-up operation of the October 2004 Puget Sound oil-spill shows:

CPCF Method—Maximum rate for clean-up and remediation of crude oil #1,and/or #2:

-   -   ≈27.86 gal/hr/worker→≈222.88 gal/day/worker vs.    -   Puget Sound (Dalco Passage)−Maximum rate, clean-up/remediation        of crude oil (type=?):    -   1.488 gal/hr/worker→11.905 gal/day/worker (84 day estimate)    -   1.078 gal/hr/worker→8.62 gal/day/worker (116 day revised        estimate)

Likewise a comparative analysis of clean-up or remediation rates, andthe performance advantage (relative increase in efficiency) shows theCPCF based technology has the capacity to out-perform the methodemployed in the Puget Sound (Dalco Passage) spill, operating 8-10 hr/dayand 7 days/week and shows for the 84 day clean-up:

-   -   222.88 gal/day÷11.905 gal/day=1,872% or 18.72× faster    -   →CPCF Technology has capacity for remediation of crude oil at a        rate of 18.72 times or 1,872% faster than the method employed in        the Puget Sound remediation operation (if completed in 84 days)        and with a relative efficiency increase performance advantage)        in the CPCF technology of:

(222.88 gal/day−11.905 gal/day)+11.905 gal/day=1,772% or 17.723× aseffective

Now, considering the revised rate of clean-up/remediation for PugetSound, with a completion time of 116 days, the CPCF rate is higher by:

222.88 gal/day÷8.62 gal/day=2,586% or 25.856× faster

with a relative efficiency increase (performance advantage) in the CPCFtechnology of:

(222.88 gal/day÷8.62 gal/day)/8.62 gal/day=2,486% or 24.856× aseffective

The data may be summarized as follows:

TABLE 1 CPCF REMEDIATION RATES vs. EXXON-VALDES (1989) AND PUGET SOUND(2005) SPILLS, AND AVERAGE PUBLISHED RATES REMEDIATED RATE: EXXON- RATE:PUGET RATE: AVG SUBSTANCE RATE: CPCF VALDES SPILL SOUND SPILL PUBLISHEDClass-1: Crude Oils 27.86 gal/hr ≦1.0 gal/hr 1.078-1.488 4-4.5 gal/hr#1, #2; Motor Oils: (per worker) (per worker) gal/hr (per worker) 5, 10,20, 30W; (per worker) Blends: 5-20W, 10-30W Class-2: Crude Oil19.84-22.78 N/A N/A 4-4.5 gal/hr #3; Motor Oils: gal/hr (per worker) 50WBlends: 20-50W (per worker) Class-3: Vegetable Oils: 17.22-23.62 N/A N/A≦3.25 gal/hr Corn, Soy, Olive, gal/hr (per worker) Safflower (perworker) Class-4: Mineral Oils 25.03 gal/hr N/A N/A N/A (per worker)Class-5: Synthetic Oils 8.5 gal/hr N/A N/A N/A (per hour)

Various features of the system may be implemented in hardware, software,or a combination of hardware and software. For example, some features ofthe system may be implemented in computer programs executing onprogrammable computers. Each program may be implemented in a high levelprocedural or object-oriented programming language to communicate with acomputer system or other machine. Furthermore, each such computerprogram may be stored on a storage medium such as read-only-memory (ROM)readable by a general or special purpose programmable computer orprocessor, for configuring and operating the computer to perform thefunctions described above.

A number of implementations have been described. Nevertheless, it willbe understood that various modifications may be made without departingfrom the spirit and scope of the invention. Accordingly, otherimplementations are within the scope of the claims.

1. A buoyant immiscible pollutant remediation apparatus for use in abody of water comprising: an upper platform; a cryogenic fluid sourceadapted for providing a cryogenic fluid, the cryogenic fluid sourcesupported by the upper platform; a lower platform disposed below theupper platform; a waste tank adapted for storing collected immisciblepollutant, the waste tank having an opening adapted for receiving thecollected immiscible pollutant, the opening disposed between the upperplatform and the lower platform; a flexible apron surroundingsubstantially the entire perimeter of the lower platform, the flexibleapron extending from a first point at the perimeter of the lowerplatform to a second point proximate to the surface of the water; atleast one cryogenic fluid dispenser coupled to the cryogenic fluidsource and adapted to dispense cryogenic fluid, in a substantiallycondensed phase, in the region proximate to the second point; at leastone collector basket coupled to an arm, the collector basket adapted totravel from a point proximate to the second point to a point proximateto the opening of the waste tank, thereby transporting at least someimmiscible pollutant that was exposed to the substantially condensedphase cryogenic fluid into the waste tank.
 2. The apparatus of claim 1comprising a lower structure disposed below the lower platform.
 3. Theapparatus of claim 2 wherein the lower structure comprises sponsons. 4.The apparatus of claim 1 comprising at least one pneumatic riser coupledto the lower structure and the upper platform, the at least onepneumatic riser adapted to expand or contract in a directionsubstantially perpendicular to the surface of the water.
 5. Theapparatus of claim 4 wherein the opening of the waste tank is coupled tothe upper platform so that the location of the opening of the waste tankis due at least in part to the expansion or contraction of the at leastone pneumatic riser.
 6. The apparatus of claim 4 wherein the lowerplatform has a circular perimeter.
 7. The apparatus of claim 6 whereinthe flexible apron has a circular perimeter.
 8. The apparatus of claim 4comprising: one or more sensors disposed proximate to the immisciblepollutant adapted to generate one or more data signals; a controllercoupled to the sensors and cryogenic fluid source, wherein thecontroller is adapted to control the cryogenic fluid source in responseto the one or more data signals.
 9. The apparatus of claim 8 wherein theone or more sensors includes an infrared sensor.
 10. The apparatus ofclaim 8 wherein the one or more sensors includes an optoacoustic sensor.11. The apparatus of claim 8 wherein the one or more sensors includes atemperature sensor.
 12. The apparatus of claim 4 comprising wirelesscommunication structure.
 13. The apparatus of claim 12 wherein thewireless communication structure includes GPS, RF or IR receivers. 14.The apparatus of claim 12 wherein the wireless communication structureincludes GPS, RF or IR transmitters.
 15. The apparatus of claim 4further comprising cryogenic fluid transport means, coupled between thecryogenic fluid source and the at least one cryogenic fluid dispenser,for maintaining the pressure of the cryogenic fluid transported to thecryogenic fluid dispenser at less than about 50 psi.
 16. The apparatusof claim 4 wherein the at least one cryogenic fluid dispenser dispensesthe cryogenic fluid at about atmospheric pressure.
 17. The apparatus ofclaim 4 wherein the at least one cryogenic fluid dispenser comprises asparger bar.
 18. The apparatus of claim 17 wherein the sparger bar isconstructed of a sintered metal.
 19. The apparatus of claim 18 whereinthe metal comprises brass, bronze or stainless steel.
 20. The apparatusof claim 17 wherein the sparger bar is constructed of a sinteredcomposite.
 21. The apparatus of claim 17 wherein the sparger bar isconstructed of a sintered material comprising silicon carbide.
 22. Theapparatus of claim 17 wherein the mean porosity of the sparger bar isbetween about 1 micron and 10 microns.
 23. The apparatus of claim 4wherein the cryogenic fluid dispenser comprises a spray bar comprisingat least one nozzle.
 24. The apparatus of claim 23 comprising means foradjusting an aperture size of at least one nozzle.
 25. The apparatus ofclaim 4 wherein the cryogenic fluid dispenser comprises a drizzle barcomprising at least one hole array.
 26. The apparatus of claim 25wherein the at least one hole array comprises holes having a diameterfrom about 0.1 millimeters to about 0.5 millimeters.